Antifouling and hydrogen sulfide scavenging compositions

ABSTRACT

Disclosed herein are scavenging and antifouling compositions useful in applications relating to the production, transportation, storage, and separation of crude oil and natural gas. Also disclosed herein are methods of using the compositions as scavengers and antifoulants, particularly in applications relating to the production, transportation, storage, and separation of crude oil and natural gas.

FIELD

The present disclosure relates generally to scavengers of sulfur-basedspecies, and more particularly to compositions for scavengingsulfur-containing compounds, such as hydrogen sulfide and/or mercaptans,and preventing fouling.

BACKGROUND

The removal of sulfur-based species from liquid or gaseous hydrocarbonstreams is a problem that has long challenged many industries. Hydrogensulfide is a problem in the oil industry, particularly in the drilling,production, transportation, storage, and processing of crude oil, aswell as waste water associated with crude oil. The same problems existin the natural gas industry and geothermal power plants.

The presence of sulfur-containing compounds, such as hydrogen sulfide,can result in the deposition of sulfur containing salts, which can causeplugging and corrosion of transmission pipes, valves, regulators andother process equipment. Even flared natural gas needs to be treated toavoid acid rain generation due to SO_(x) formation. Also, in themanufactured gas industry or coke making industry, coal-gas emissionscontaining unacceptable levels of hydrogen sulfide are commonly producedfrom destructive distillation of bituminous coal.

Since hydrogen sulfide has an offensive odor and natural gas containingit is called “sour” gas, treatments to lower hydrogen sulfide are termed“sweetening” processes. When a particular compound is used to remove orlower H₂S, it is called scavenging agent or scavenger.

BRIEF SUMMARY

In one aspect, compositions are disclosed that include a Michaelacceptor and one or more compounds of formula (I),

The R¹, R², and R³ groups may be each independently selected from thegroup consisting of hydrogen, alkylenyl, alkenylenyl, alkynylenyl,alkyl, alkenyl, and alkynyl, wherein said alkylenyl, alkenylenyl,alkynylenyl, alkyl, alkenyl, and alkynyl are each independently, at eachoccurrence, substituted or unsubstituted with one or more suitablesubstituents. The variables k, l, and m may be each independently aninteger selected from the group consisting of 0 to 25, wherein k+l+mis >0. The variables x, y, and z may be each independently an integerselected from the group consisting of 0 and 1, wherein x+y+z is 1, 2, or3.

When x is 0, R¹ may be hydrogen, alkyl, alkenyl, or alkynyl. When x is1, R¹ may be alkylenyl, alkenylenyl, or alkynylenyl. When y is 0, R² maybe hydrogen, alkyl, alkenyl, or alkynyl. When y is 1, R² may bealkylenyl, alkenylenyl, or alkynylenyl. When z is 0, R³ may be hydrogen,alkyl, alkenyl, or alkynyl. When z is 1, R³ may be alkylenyl,alkenylenyl, or alkynylenyl.

In some embodiments, x+y+z is 3 and R¹, R², and R³ are each alkylenyl.In some embodiments, x+y+z is 3 and R¹, R², and R³ are eachC₂-alkylenyl. In some embodiments, x+y+z is 3 and R¹, R², and R³ areeach unsubstituted C₂-alkylenyl. In some embodiments, x is 1, y is 1, zis 0, R¹ and R² are each alkylenyl, and R³ is alkyl. In someembodiments, x is 1, y is 1, z is 0, R¹ and R² are each C₂-alkylenyl,and R³ is C₁-alkyl. In some embodiments, x is 1, y is 1, z is 0, R¹ andR² are each unsubstituted C₂-alkylenyl, and R³ is unsubstitutedC₁-alkyl. In some embodiments, x is 1, y is 1, z is 0, R¹ and R² areeach alkylenyl, and R³ is hydrogen. In some embodiments, x is 1, y is 1,z is 0, R¹ and R² are each C₂-alkylenyl, and R³ is hydrogen. In someembodiments, x is 1, y is 1, z is 0, R¹ and R² are each unsubstitutedC₂-alkylenyl, and R³ is hydrogen.

In some embodiments, the compound comprises formula (II):

wherein R³ is selected from the group consisting of hydrogen, alkylenyl,alkenylenyl, alkynylenyl, alkyl, alkenyl, and alkynyl, wherein saidalkylenyl, alkenylenyl, alkynylenyl, alkyl, alkenyl, and alkynyl areeach independently substituted or unsubstituted with one or moresuitable substituents; k, l, and m are each independently an integerselected from the group consisting of 0 to 25, wherein k+l+m is >0; andz is 0 or 1; provided that when z is 1, R³ is alkylenyl, alkenylenyl, oralkynylenyl; when z is 0, R³ is hydrogen, alkyl, alkenyl, or alkynyl;and when z is 1, k is 1, l is 1, and m is 1, then R³ is not anunsubstituted C₂-alkylenyl.

In some embodiments, the compound comprises formula (III):

wherein k, l, and m are each 1.

In some embodiments, the Michael acceptor is an α, β-unsaturatedcarbonyl compound. In some embodiments, the Michael acceptor is selectedfrom the group consisting of acrylic acid, acrylamide, methacrylate,dimethyl maleate, crotonaldehyde, 3-butene-2-one, and any combinationthereof. In some embodiments, the Michael acceptor is acrylic acid.

In some embodiments, the composition comprises an additive selected fromthe group consisting of sulfate, sulfate salt, thiosulfate, thiosulfatesalt, and any combination thereof. In some embodiments, the compositioncomprises sodium thiosulfate pentahydrate.

In some embodiments, the composition further comprises a compoundselected from the group consisting of alkyl benzyl ammonium chloride,benzyl cocoalkyl(C₁₂-C₁₈)dimethylammonium chloride, dicocoalkyl(C₁₂-C₁₈)dimethylammonium chloride, ditallow dimethylammonium chloride,di(hydrogenated tallow alkyl)dimethyl quaternary ammonium methylchloride, methyl bis(2-hydroxyethyl cocoalkyl(C₁₂-C₁₈) quaternaryammonium chloride, dimethyl(2-ethyl) tallow ammonium methyl sulfate,n-dodecylbenzyldimethylammonium chloride, n-octadecylbenzyldimethylammonium chloride, n-dodecyltrimethylammonium sulfate, soyaalkyltrimethylammonium chloride, and hydrogenated tallow alkyl(2-ethylhyexyl) dimethyl quaternary ammonium methyl sulfate, and anycombination thereof.

In another aspect, disclosed are methods including the step of adding acomposition to a fluid or gas stream. The composition includes a Michaelacceptor and one or more compounds of formula (I),

The variables R¹, R², and R³ may be each independently selected from thegroup consisting of hydrogen, alkylenyl, alkenylenyl, alkynylenyl,alkyl, alkenyl, and alkynyl, wherein said alkylenyl, alkenylenyl,alkynylenyl, alkyl, alkenyl, and alkynyl are each independently, at eachoccurrence, substituted or unsubstituted with one or more suitablesubstituents. The variables k, l, and m may be each independently aninteger selected from the group consisting of 0 to 25, wherein k+l+m>0.The variables x, y, and z may be each independently an integer selectedfrom the group consisting of 0 and 1, wherein x+y+z is 1, 2, or 3.

When x is 0, R¹ may be hydrogen, alkyl, alkenyl, or alkynyl. When x is1, R¹ is alkylenyl, alkenylenyl, or alkynylenyl. When y is 0, R² may behydrogen, alkyl, alkenyl, or alkynyl. When y is 1, R² may be alkylenyl,alkenylenyl, or alkynylenyl. When z is 0, R³ may be hydrogen, alkyl,alkenyl, or alkynyl. When z is 1, R³ may be alkylenyl, alkenylenyl, oralkynylenyl.

In some embodiments, x+y+z is 3 and R¹, R², and R³ are each alkylenyl.In some embodiments, x+y+z is 3 and R¹, R², and R³ are eachC₂-alkylenyl. In some embodiments, x+y+z is 3, and R¹, R², and R³ areeach unsubstituted C₂-alkylenyl. In some embodiments, x is 1, y is 1, zis 0, R¹ and R² are each alkylenyl, and R³ is alkyl. In someembodiments, x is 1, y is 1, z is 0, R¹ and R² are each C₂-alkylenyl,and R³ is C₁-alkyl. In some embodiments, x is 1, y is 1, z is 0, R¹ andR² are each unsubstituted C₂-alkylenyl, and R³ is unsubstitutedC₁-alkyl. In some embodiments, x is 1, y is 1, z is 0, R¹ and R² areeach alkylenyl, and R³ is hydrogen. In some embodiments, x is 1, y is 1,z is 0, R¹ and R² are each C₂-alkylenyl, and R³ is hydrogen. In someembodiments, x is 1, y is 1, z is 0, R¹ and R² are each unsubstitutedC₂-alkylenyl, and R³ is hydrogen.

In some embodiments, the compound comprises formula (II),

wherein R³ is selected from the group consisting of hydrogen, alkylenyl,alkenylenyl, alkynylenyl, alkyl, alkenyl, and alkynyl, wherein saidalkylenyl, alkenylenyl, alkynylenyl, alkyl, alkenyl, and alkynyl areeach independently substituted or unsubstituted with one or moresuitable substituents; k, l, and m are each independently an integerselected from the group consisting of 0 to 25, wherein k+l+m is >0; andz is 0 or 1; provided that when z is 1, R³ is alkylenyl, alkenylenyl, oralkynylenyl; when z is 0, R³ is hydrogen, alkyl, alkenyl, or alkynyl;and when z is 1, k is 1, l is 1, and m is 1, then R³ is not anunsubstituted C₂-alkylenyl.

In some embodiments, the compound comprises formula (III):

wherein k, l, and m are each 1.

In some embodiments, the Michael acceptor is an α, β-unsaturatedcarbonyl compound. In some embodiments, the Michael acceptor is selectedfrom the group consisting of acrylic acid, acrylamide, methacrylate,dimethyl maleate, crotonaldehyde, 3-butene-2-one, and any combinationthereof. In some embodiments, the Michael acceptor is acrylic acid.

In some embodiments, the composition comprises an additive selected fromthe group consisting of sulfate, sulfate salt, thiosulfate, thiosulfatesalt, and any combination thereof. In some embodiments, the compositioncomprises sodium thiosulfate pentahydrate.

In some embodiments, the composition further comprises a compoundselected from the group consisting of alkyl benzyl ammonium chloride,benzyl cocoalkyl(C₁₂-C₁₈)dimethylammonium chloride, dicocoalkyl(C₁₂-C₁₈)dimethylammonium chloride, ditallow dimethylammonium chloride,di(hydrogenated tallow alkyl)dimethyl quaternary ammonium methylchloride, methyl bis(2-hydroxyethyl cocoalkyl(C₁₂-C₁₈) quaternaryammonium chloride, dimethyl(2-ethyl) tallow ammonium methyl sulfate,n-dodecylbenzyldimethylammonium chloride, n-octadecylbenzyldimethylammonium chloride, n-dodecyltrimethylammonium sulfate, soyaalkyltrimethylammonium chloride, and hydrogenated tallow alkyl(2-ethylhyexyl) dimethyl quaternary ammonium methyl sulfate, and anycombination thereof.

In some embodiments, the composition is added to a liquid in a processunit selected from the group consisting of a falling film column, abubble column spray tower, a gas-liquid agitated vessel, a plate column,a rotating disc contactor, a contact tower, a wet flue gas desulfurizer,a spray dry absorber, a dry sorbent injector, a spray tower, a bubbletower and a venturi tube. In some embodiments, the composition is addedto a liquid in a contact tower.

The foregoing has outlined rather broadly the features and technicaladvantages of the present disclosure in order that the detaileddescription that follows may be better understood. Additional featuresand advantages of the disclosure will be described hereinafter that formthe subject of the claims of this application. It should be appreciatedby those skilled in the art that the conception and the specificembodiments disclosed may be readily utilized as a basis for modifyingor designing other embodiments for carrying out the same purposes of thepresent disclosure. It should also be realized by those skilled in theart that such equivalent embodiments do not depart from the spirit andscope of the disclosure as set forth in the appended claims.

DETAILED DESCRIPTION

Disclosed herein are hydrogen sulfide and/or mercaptan scavenging andantifouling compositions, methods of using those compositions, andprocesses for their preparation. The compositions are useful in thecontrol of hydrogen sulfide and/or mercaptan emissions from crude oilbased, natural gas based, and coal based products and processes. Thecompositions are particularly useful in preventing solid deposits inprocess equipment used for scavenging hydrogen sulfide and/or mercaptanchemicals. The compositions are applicable to both upstream anddownstream processes. The scavenging compositions, optionally blendedwith aqueous and/or non-aqueous solvents, are useful in a wide range ofclimates and under a wide range of process conditions.

The disclosed processes for preparing the compositions are economic,waste free, and provide said compounds in quantitative yields. Thecompositions can optionally be blended with hydrophilic solvents (e.g.,alcohols, glycol, polyols) for non-aqueous applications. Alternatively,the compositions may be blended with an aqueous phase for direct use inaqueous applications.

The compositions provide further economic advantages through reducedtransportation costs due to increased actives concentration, and throughincreased production capacity. The compositions also considerably lowerthe water washable nitrogen content to eliminate nitrogen contaminationof refinery catalyst beds. The compositions also provide the ability tomanufacture the products at most locations without offensive odoremanating from raw materials. The compositions, when in contact withhydrogen sulfide, produce reaction product waste that can be addeddirectly to waste water; whereas, processes that employ the hydrogensulfide scavenger triazine require expensive hazardous waste removal.

The compositions prevent the reaction product waste from forming soliddeposits in the tower, pipeline, or the like; thereby prolongingequipment operation time and improving H₂S removal. Without being boundby theory, solid deposits form, for example from the formation ofpolymethylene sulfide in the reaction product waste. Solid depositformation leads to clogging requiring process interruption for solidsremoval and cleaning.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art. In case of conflict, the present document, includingdefinitions, will control. Preferred methods and materials are describedbelow, although methods and materials similar or equivalent to thosedescribed herein can be used in practice or testing of the presentinvention. The materials, methods, and examples disclosed herein areillustrative only and not intended to be limiting.

The terms “comprise(s),” “include(s),” “having,” “has,” “can,”“contain(s),” and variants thereof, as used herein, are intended to beopen-ended transitional phrases, terms, or words that do not precludethe possibility of additional acts or structures. The singular forms“a,” “and” and “the” include plural references unless the contextclearly dictates otherwise. The present disclosure also contemplatesother embodiments “comprising,” “consisting of” and “consistingessentially of,” the embodiments or elements presented herein, whetherexplicitly set forth or not.

In accordance with the present disclosure, the phrases “consistessentially of,” “consists essentially of,” “consisting essentially of,”and the like limit the scope of a claim to the specified materials orsteps and those materials or steps that do not materially affect thebasic and novel characteristic(s) of the claimed invention.

The term “suitable substituent,” as used herein, is intended to mean achemically acceptable functional group, preferably a moiety that doesnot negate the hydrogen sulfide scavenging activity of the inventivecompounds. Such suitable substituents include, but are not limited tohalo groups, perfluoroalkyl groups, perfluoroalkoxy groups, alkylgroups, alkenyl groups, alkynyl groups, hydroxy groups, oxo groups,mercapto groups, alkylthio groups, alkoxy groups, aryl or heteroarylgroups, aryloxy or heteroaryloxy groups, aralkyl or heteroaralkylgroups, aralkoxy or heteroaralkoxy groups, HO—(C═O)— groups, heterocylicgroups, cycloalkyl groups, amino groups, alkyl- and dialkylamino groups,carbamoyl groups, alkylcarbonyl groups, alkoxycarbonyl groups,alkylaminocarbonyl groups, dialkylamino carbonyl groups, arylcarbonylgroups, aryloxycarbonyl groups, alkylsulfonyl groups, arylsulfonylgroups, groups of formula —(OCH₂)_(t)OH wherein t is 1 to 25, and groupsof formula -alkylenyl-(OCH₂)_(t)OH wherein t is 1 to 25. Those skilledin the art will appreciate that many substituents can be substituted byadditional substituents.

The term “alkyl,” as used herein, refers to a linear or branchedhydrocarbon radical, preferably having 1 to 32 carbon atoms (i.e., 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22,23, 24, 25, 26, 27, 28, 39, 30, 31, or 32 carbons). Alkyl groupsinclude, but are not limited to, methyl, ethyl, n-propyl, isopropyl,n-butyl, iso-butyl, secondary-butyl, and tertiary-butyl. Alkyl groupsmay be unsubstituted or substituted by one or more suitablesubstituents, as defined above.

The term “alkylenyl” or “alkylene,” as used herein, refers to a divalentgroup derived from a saturated, straight or branched hydrocarbon chainof from 1 to 32 carbon atoms. The term “C₁-C₆ alkylene” means thosealkylene or alkylenyl groups having from 1 to 6 carbon atoms.Representative examples of alkylenyl groups include, but are not limitedto, —CH₂—, —CH(CH₃)—, —CH(C₂H₅)—, —CH(CH(CH₃)(C₂H₅))—,—C(H)(CH₃)CH₂CH₂—, —C(CH₃)₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, —CH₂CH₂CH₂CH₂—, and—CH₂CH(CH₃)CH₂—. Alkylenyl groups may be unsubstituted or substituted byone or more suitable substituents, as defined above.

The term “alkenyl,” as used herein, refers to a straight or branchedhydrocarbon radical, preferably having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39,30, 31, or 32 carbons, and having one or more carbon-carbon doublebonds. Alkenyl groups include, but are not limited to, ethenyl,1-propenyl, 2-propenyl (allyl), iso-propenyl, 2-methyl-1-propenyl,1-butenyl, and 2-butenyl. Alkenyl groups may be unsubstituted orsubstituted by one or more suitable substituents, as defined above.

The term “alkenylenyl” or “alkenylene,” as used herein, refers to adivalent group derived from a straight or branched chain hydrocarbon of2 to 32 carbon atoms, which contains at least one carbon-carbon doublebond. Representative examples of alkenylenyl groups include, but are notlimited to, —C(H)═C(H)—, —C(H)═C(H)—CH₂—, —C(H)═C(H)—CH₂—CH₂—,—CH₂—C(H)═C(H)—CH₂—, —C(H)═C(H)—CH(CH₃)—, and—CH₂—C(H)═C(H)—CH(CH₂CH₃)—. Alkenylenyl groups may be unsubstituted orsubstituted by one or more suitable substituents, as defined above.

The term “alkynyl,” as used herein, refers to a straight or branchedhydrocarbon radical, preferably having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39,30, 31, or 32 carbons, and having one or more carbon-carbon triplebonds. Alkynyl groups include, but are not limited to, ethynyl,propynyl, and butynyl. Alkynyl groups may be unsubstituted orsubstituted by one or more suitable substituents, as defined above.

The term “alkynylenyl” or “alkynylene,” as used herein, refers to adivalent unsaturated hydrocarbon group which may be linear or branchedand which has at least one carbon-carbon triple bond. Representativeexamples of alkynylenyl groups include, but are not limited to, —C≡C—,—C≡C—CH₂—, —C≡C—CH₂—CH₂—, —CH₂—C≡C—CH₂—, —C≡C—CH(CH₃)—, and—CH₂—C≡C—CH(CH₂CH₃)—. Alkynylenyl groups may be unsubstituted orsubstituted by one or more suitable substituents, as defined above.

The term “alkoxy,” as used herein, refers to an alkyl group, as definedherein, appended to the parent molecular moiety through an oxygen atom.

The term “aryl,” as used herein, means monocyclic, bicyclic, ortricyclic aromatic radicals such as phenyl, naphthyl,tetrahydronaphthyl, indanyl and the like; optionally substituted by oneor more suitable substituents, preferably 1 to 5 suitable substituents,as defined above.

The term “carbonyl,” “(C═O),” or “—C(O)—” (as used in phrases such asalkylcarbonyl, alkyl —(C═O)— or alkoxycarbonyl) refers to the joinder ofthe >C═O moiety to a second moiety such as an alkyl or amino group (i.e.an amido group). Alkoxycarbonylamino (i.e. alkoxy(C═O)—NH—) refers to analkyl carbamate group. The carbonyl group is also equivalently definedherein as (C═O). Alkylcarbonylamino refers to groups such as acetamide.

The term “cycloalkyl,” as used herein, refers to a mono, bicyclic ortricyclic carbocyclic radical (e.g., cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,cyclopentenyl, cyclohexenyl, bicyclo[2.2.1]heptanyl,bicyclo[3.2.1]octanyl and bicyclo[5.2.0]nonanyl, etc.); optionallycontaining 1 or 2 double bonds. Cycloalkyl groups may be unsubstitutedor substituted by one or more suitable substituents, preferably 1 to 5suitable substituents, as defined above.

The term “halo” or “halogen,” as used herein, refers to a fluoro,chloro, bromo or iodo radical.

The term “heteroaryl,” as used herein, refers to a monocyclic, bicyclic,or tricyclic aromatic heterocyclic group containing one or moreheteroatoms selected from O, S and N in the ring(s). Heteroaryl groupsinclude, but are not limited to, pyridyl, pyrazinyl, pyrimidinyl,pyridazinyl, thienyl, furyl, imidazolyl, pyrrolyl, oxazolyl (e.g.,1,3-oxazolyl, 1,2-oxazolyl), thiazolyl (e.g., 1,2-thiazolyl,1,3-thiazolyl), pyrazolyl, tetrazolyl, triazolyl (e.g., 1,2,3-triazolyl,1,2,4-triazolyl), oxadiazolyl (e.g., 1,2,3-oxadiazolyl), thiadiazolyl(e.g., 1,3,4-thiadiazolyl), quinolyl, isoquinolyl, benzothienyl,benzofuryl, and indolyl. Heteroaryl groups may be unsubstituted orsubstituted by one or more suitable substituents, preferably 1 to 5suitable substituents, as defined above.

The term “heterocycle,” as used herein, refers to a monocyclic,bicyclic, or tricyclic group containing 1 to 4 heteroatoms selected fromN, O, S(O)_(n), P(O)_(n), PR^(x), NH or NR^(x), wherein R^(x) is asuitable substituent. Heterocyclic groups optionally contain 1 or 2double bonds. Heterocyclic groups include, but are not limited to,azetidinyl, tetrahydrofuranyl, imidazolidinyl, pyrrolidinyl,piperidinyl, piperazinyl, oxazolidinyl, thiazolidinyl, pyrazolidinyl,thiomorpholinyl, tetrahydrothiazinyl, tetrahydro-thiadiazinyl,morpholinyl, oxetanyl, tetrahydrodiazinyl, oxazinyl, oxathiazinyl,indolinyl, isoindolinyl, quinuclidinyl, chromanyl, isochromanyl, andbenzoxazinyl. Examples of monocyclic saturated or partially saturatedring systems are tetrahydrofuran-2-yl, tetrahydrofuran-3-yl,imidazolidin-1-yl, imidazolidin-2-yl, imidazolidin-4-yl,pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, piperidin-1-yl,piperidin-2-yl, piperidin-3-yl, piperazin-1-yl, piperazin-2-yl,piperazin-3-yl, 1,3-oxazolidin-3-yl, isothiazolidine,1,3-thiazolidin-3-yl, 1,2-pyrazolidin-2-yl, 1,3-pyrazolidin-1-yl,thiomorpholin-yl, 1,2-tetrahydrothiazin-2-yl,1,3-tetrahydrothiazin-3-yl, tetrahydrothiadiazin-yl, morpholin-yl,1,2-tetrahydrodiazin-2-yl, 1,3-tetrahydrodiazin-1-yl, 1,4-oxazin-2-yl,and 1,2,5-oxathiazin-4-yl. Heterocyclic groups may be unsubstituted orsubstituted by one or more suitable substituents, preferably 1 to 3suitable substituents, as defined above.

The term “hydroxy,” as used herein, refers to an —OH group.

The term “oxo,” as used herein, refers to a double bonded oxygen (═O)radical wherein the bond partner is a carbon atom. Such a radical canalso be thought as a carbonyl group.

The term “counterion,” as used herein, means a halide (e.g., fluoride,chloride, bromide, iodide), a carboxylate anion, such as selected fromdeprotonation of mineral acid, acrylic acid, acetic acid, methacrylicacid, glycolic acid, thioglycolic acid, propionic acid, butyric acid,and the like, or any other anionic constituent that satisfies the chargebalance necessary to form a neutral molecule.

The term “sweetening,” as used herein, may refer to a process thatremoves sulfur species from a gas or liquid. The sulfur species mayinclude hydrogen sulfide and mercaptans.

The term “sour gas,” as used herein, may refer to a gas that includessignificant amounts of sulfur species, such as hydrogen sulfide and/ormercaptans.

The term “sour liquid” or “sour fluid,” as used herein, may refer to aliquid that includes significant amounts of sulfur species, such ashydrogen sulfide and/or mercaptans.

The term “water cut,” as used herein, means the percentage of water in acomposition containing an oil and water mixture.

Useful compounds that can be used in the compositions include scavengersof sulfur-based species such as hydrogen sulfide and mercaptans. Thecompounds may be particularly useful in the oil, gas, and coalindustries. The compounds may be alkanolamine formaldehyde additionproducts. The alkanolamine formaldedhyde addition products may beprovided in anhydrous or hydrous form.

In one aspect, useful compounds in the compositions are of formula (I),

wherein R¹, R², and R³ are each independently selected from the groupconsisting of hydrogen, alkylenyl, alkenylenyl, alkynylenyl, alkyl,alkenyl, and alkynyl, wherein said alkylenyl, alkenylenyl, alkynylenyl,alkyl, alkenyl, and alkynyl are each independently, at each occurrence,substituted or unsubstituted with one or more suitable substituents; k,l, and m are each independently an integer selected from the groupconsisting of 0 to 25, wherein k+l+m is >0; and x, y, and z are eachindependently an integer selected from the group consisting of 0 and 1,wherein x+y+z is 1, 2, or 3.

In some embodiments, when x is 0, R¹ is hydrogen, alkyl, alkenyl, oralkynyl; and when x is 1, R¹ is alkylenyl, alkenylenyl, or alkynylenyl.In some embodiments, when y is 0, R² is hydrogen, alkyl, alkenyl, oralkynyl; and when y is 1, R² is alkylenyl, alkenylenyl, or alkynylenyl.In some embodiments, when z is 0, R³ is hydrogen, alkyl, alkenyl, oralkynyl; and when z is 1, R³ is alkylenyl, alkenylenyl, or alkynylenyl.

It is to be understood that when x is 0, [(OCH₂)_(k)OH] is absent; wheny is 0, [(OCH₂)_(l)OH] is absent; and when z is 0, [(OCH₂)_(m)OH] isabsent. It is also to be understood that when R¹ is alkylenyl,alkenylenyl, or alkynylenyl, then x must be 1; when R¹ is hydrogen,alkyl, alkenyl, or alkynyl, then x must be 0; when R² is alkylenyl,alkenylenyl, or alkynylenyl, then y must be 1; when R² is hydrogen,alkyl, alkenyl, or alkynyl, then y must be 0; when R³ is alkylenyl,alkenylenyl, or alkynylenyl, then z must be 1; and when R³ is hydrogen,alkyl, alkenyl, or alkynyl, then z must be 0.

It is also to be understood that when k>0, then x must be 1; when l>0,then y must be 1; and when m is >0, then z must be 1.

In certain embodiments, one or more of R¹, R², and R³ are straight chainalkylenyl. In certain embodiments, one or more of R¹, R², and R³ arebranched alkylenyl. In certain embodiments, one or more of R¹, R², andR³ are unsubstituted alkylenyl. In certain embodiments, one or more ofR¹, R², and R³ are substituted alkylenyl. In certain embodiments, one ormore of R¹, R², and R³ are straight chain, unsubstituted alkylenyl. Incertain embodiments, one or more of R¹, R², and R³ are straight chain,substituted alkylenyl. In certain embodiments, one or more of R¹, R²,and R³ are branched, unsubstituted alkylenyl. In certain embodiments,one or more of R¹, R², and R³ are branched, substituted alkylenyl.

In certain embodiments, R¹, R², and R³ are each straight chainalkylenyl. In certain embodiments, R¹, R², and R³ are each branchedalkylenyl. In certain embodiments, R¹, R², and R³ are each unsubstitutedalkylenyl. In certain embodiments, R¹, R², and R³ are each substitutedalkylenyl. In certain embodiments, R¹, R², and R³ are each straightchain, unsubstituted alkylenyl. In certain embodiments, R¹, R², and R³are each straight chain, substituted alkylenyl. In certain embodiments,R¹, R², and R³ are each branched, unsubstituted alkylenyl. In certainembodiments, R¹, R², and R³ are each branched, substituted alkylenyl.

In certain embodiments, R¹, R², and R³ are each C₁-C₃₂-alkylenyl. Incertain embodiments, R¹, R², and R³ are each C₁-C₂₄-alkylenyl. Incertain embodiments, R¹, R², and R³ are each C₁-C₁₀ alkylenyl. Incertain embodiments, R¹, R², and R³ are each C₁-C₆-alkylenyl.

In certain embodiments, one or more of R¹, R², and R³ are C₁-alkylenyl.In certain embodiments, one or more of R¹, R², and R³ are unsubstitutedC₁-alkylenyl. In certain embodiments, one or more of R¹, R², and R³ aresubstituted C₁-alkylenyl. In certain embodiments, one or more of R¹, R²,and R³ are C₂-alkylenyl. In certain embodiments, one or more of R¹, R²,and R³ are unsubstituted C₂-alkylenyl. In certain embodiments, one ormore of R¹, R², and R³ are substituted C₂-alkylenyl. In certainembodiments, one or more of R¹, R², and R³ are C₃-alkylenyl. In certainembodiments, one or more of R¹, R², and R³ are unsubstitutedC₃-alkylenyl. In certain embodiments, one or more of R¹, R², and R³ aresubstituted C₃-alkylenyl. In certain embodiments, one or more of R¹, R²,and R³ are C₄-alkylenyl. In certain embodiments, one or more of R¹, R²,and R³ are unsubstituted C₄-alkylenyl. In certain embodiments, one ormore of R¹, R², and R³ are substituted C₄-alkylenyl. In certainembodiments, one or more of R¹, R², and R³ are C₅-alkylenyl. In certainembodiments, one or more of R¹, R², and R³ are unsubstitutedC₅-alkylenyl. In certain embodiments, one or more of R¹, R², and R³ aresubstituted C₅-alkylenyl. In certain embodiments, one or more of R¹, R²,and R³ are C₆-alkylenyl. In certain embodiments, one or more of R¹, R²,and R³ are unsubstituted C₆-alkylenyl. In certain embodiments, one ormore of R¹, R², and R³ are substituted C₆-alkylenyl.

In certain embodiments, R¹, R², and R³ are each C₁-alkylenyl. In certainembodiments, R¹, R², and R³ are each unsubstituted C₁-alkylenyl. Incertain embodiments, R¹, R², and R³ are each substituted C₁-alkylenyl.In certain embodiments, R¹, R², and R³ are each C₂-alkylenyl. In certainembodiments, R¹, R², and R³ are each unsubstituted C₂-alkylenyl. Incertain embodiments, R¹, R², and R³ are each substituted C₂-alkylenyl.In certain embodiments, R¹, R², and R³ are each C₃-alkylenyl. In certainembodiments, R¹, R², and R³ are each unsubstituted C₃-alkylenyl. Incertain embodiments, R¹, R², and R³ are each substituted C₃-alkylenyl.In certain embodiments, R¹, R², and R³ are each C₄-alkylenyl. In certainembodiments, R¹, R², and R³ are each unsubstituted C₄-alkylenyl. Incertain embodiments, R¹, R², and R³ are each substituted C₄-alkylenyl.In certain embodiments, R¹, R², and R³ are each C₅-alkylenyl. In certainembodiments, R¹, R², and R³ are each unsubstituted C₅-alkylenyl. Incertain embodiments, R¹, R², and R³ are each substituted C₅-alkylenyl.In certain embodiments, R¹, R², and R³ are each C₆-alkylenyl. In certainembodiments, R¹, R², and R³ are each unsubstituted C₆-alkylenyl. Incertain embodiments, R¹, R², and R³ are each substituted C₆-alkylenyl.

In certain embodiments, when x is 1, y is 1, z is 1, k is 1, l is 1, andm is 1, then R¹, R², and R³ are not simultaneously unsubstitutedC₂-alkylenyl.

In certain embodiments, R¹ and R² are alkylenyl, and R³ is alkyl. Incertain embodiments, R¹ and R² are unsubstituted alkylenyl, and R³ isunsubstituted alkyl. In certain embodiments, R¹ and R² are substitutedalkylenyl, and R³ is unsubstituted alkyl. In certain embodiments, R¹ andR² are substituted alkylenyl, and R³ is substituted alkyl. In certainembodiments, R¹ and R² are unsubstituted alkylenyl, and R³ issubstituted alkyl.

In certain embodiments, R¹ and R² are C₁-C₃₂, C₁-C₁₆, C₁-C₁₀, or C₁-C₆alkylenyl, and R³ is C₁-C₃₂, C₁-C₁₆, C₁-C₁₀, or C₁-C₆ alkyl. In certainembodiments, R¹ and R² are unsubstituted C₁-C₃₂, C₁-C₁₆, C₁-C₁₀, orC₁-C₆ alkylenyl, and R³ is unsubstituted C₁-C₃₂, C₁-C₁₆, C₁-C₁₀, orC₁-C₆ alkyl. In certain embodiments, R¹ and R² are unsubstitutedC₂-alkylenyl, and R³ is unsubstituted C₁-alkyl. In certain embodiments,R¹ and R² are unsubstituted C₂-alkylenyl, and R³ is unsubstitutedC₂-alkyl.

In certain embodiments, R¹ and R² are alkylenyl, and R³ is hydrogen. Incertain embodiments, R¹ and R² are unsubstituted alkylenyl, and R³ ishydrogen. In certain embodiments, R¹ and R² are unsubstitutedC₂-alkylenyl, and R³ is hydrogen. In certain embodiments, R¹ and R² aresubstituted alkylenyl, and R³ is hydrogen. In certain embodiments, R¹and R² are substituted C₂-alkylenyl, and R³ is hydrogen.

In certain embodiments, one or more of R¹, R², and R³ are substitutedwith one or more suitable substituents selected from hydroxy, groups offormula —(OCH₂)_(t)OH wherein t is 1 to 25, and groups of formula-alkylenyl-(OCH₂)_(t)OH wherein t is 1 to 25.

In certain embodiments, k is 0 to 25, l is 0 to 25, and m is 0 to 25,provided that k+l+m is >0. In certain embodiments, k is 1 to 25, l is 1to 25, and m is 1 to 25. In certain embodiments, k is 1 to 20, l is 1 to20, and m is 1 to 20. In certain embodiments, k is 1 to 13, l is 1 to13, and m is 1 to 13. In certain embodiments, k is 1 to 10, l is 1 to10, and m is 1 to 10.

In certain embodiments, k+l+m ranges from 1 to 25. In certainembodiments, k+l+m ranges from 1 to 13. In certain embodiments, k+l+mranges from 1 to 10. In certain embodiments, k+l+m is 1, 2, 3, 4, 5, 6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or25.

In certain embodiments, x is 1, y is 1, and z is 1. In certainembodiments, x is 1, y is 1, and z is 0. In certain embodiments, x is 1,y is 0, and z is 1. In certain embodiments, x is 0, y is 1, and z is 1.In certain embodiments, x is 1, y is 0, and z is 0. In certainembodiments, x is 0, y is 1, and z is 0. In certain embodiments, x is 0,y is 0, and z is 1.

In certain embodiments, a compound has formula (II), wherein R³ isselected from the group consisting of hydrogen, alkylenyl, alkenylenyl,alkynylenyl, alkyl, alkenyl, and alkynyl, wherein said alkylenyl,alkenylenyl, alkynylenyl, alkyl, alkenyl, and alkynyl are eachindependently substituted or unsubstituted with one or more suitablesubstituents; wherein k, l, and m are each independently an integerselected from the group consisting of 0 to 25, wherein k+l+m>0; andwherein z is 0 or 1; provided that when z is 1, R³ is alkylenyl,alkenylenyl, or alkynylenyl; provided that when z is 0, R³ is hydrogen,alkyl, alkenyl, or alkynyl.

It is to be understood that when z is 0, [HO(H₂CO)_(m)] is absent. It isalso understood that when m is >0, then z must be 1. In certainembodiments, when z is 1, k is 1, and l is 1, then R³ is not anunsubstituted C₂-alkylenyl. In certain embodiments, z is 1 and R³ isalkylenyl. In certain embodiments, z is 1 and R³ is C₂-alkylenyl. Incertain embodiments, z is 1 and R³ is unsubstituted C₂-alkylenyl. Incertain embodiments, z is 0 and R³ is alkyl. In certain embodiments, zis 0 and R³ is C₁-alkyl. In certain embodiments, z is 0 and R³ isunsubstituted C₁-alkyl. In certain embodiments, z is 0 and R³ ishydrogen. In certain embodiments, k is 0 to 25, l is 0 to 25, and m is 0to 25. In certain embodiments, k is 1 to 25, l is 1 to 25, and m is 1 to25. In certain embodiments, k is 1 to 20, l is 1 to 20, and m is 1 to20. In certain embodiments, k is 1 to 13, l is 1 to 13, and m is 1 to13. In certain embodiments, k is 1 to 10, l is 1 to 10, and m is 1 to10. In certain embodiments, k+l+m ranges from 1 to 25. In certainembodiments, k+l+m ranges from 1 to 13. In certain embodiments, k+l+mranges from 1 to 10. In certain embodiments, k+l+m is 1, 2, 3, 4, 5, 6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or25. In certain embodiments, when z is 1, k is 1, l is 1, and m is 1,then R³ is not an unsubstituted C₂-alkylenyl.

In certain embodiments, a compound has formula (III), wherein k is 0 to25, l is 0 to 25, and m is 0 to 25, provided that k+l+m is >0. Incertain embodiments, k is 1 to 25, l is 1 to 25, and m is 1 to 25. Incertain embodiments, k is 1 to 20, l is 1 to 20, and m is 1 to 20. Incertain embodiments, k is 1 to 13, l is 1 to 13, and m is 1 to 13. Incertain embodiments, k is 1 to 10, l is 1 to 10, and m is 1 to 10. Incertain embodiments, k+l+m ranges from 1 to 25. In certain embodiments,k+l+m ranges from 1 to 13. In certain embodiments, k+l+m ranges from 1to 10. In certain embodiments, k+l+m is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25. Incertain embodiments, k, l, and m are not simultaneously 1.

In certain embodiments, a compound has formula (IV), wherein R³ ishydrogen, alkyl, alkenyl, or alkynyl, wherein said alkyl, alkenyl, andalkynyl are each independently substituted or unsubstituted with one ormore suitable substituents, and wherein k and l are each independentlyan integer selected from the group consisting of 0 to 25, provided thatk+l is >0. In certain embodiments, R³ is alkyl. In certain embodiments,R³ is unsubstituted C₁-alkyl or unsubstituted C₂-alkyl. In certainembodiments, R³ is hydrogen. In certain embodiments, k is 1 to 25, and lis 1 to 25. In certain embodiments, k is 1 to 20, and l is 1 to 20. Incertain embodiments, k is 1 to 13, and l is 1 to 13. In certainembodiments, k is 1 to 10, and l is 1 to 10. In certain embodiments, k+lranges from 1 to 25. In certain embodiments, k+l ranges from 1 to 13. Incertain embodiments, k+l ranges from 1 to 10. In certain embodiments,k+l is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18,19, 20, 21, 22, 23, 24, or 25.

In certain embodiments, a compound has formula (V), wherein k and l areeach independently an integer selected from the group consisting of 0 to25, provided that k+l is >0. In certain embodiments, k is 1 to 25, and lis 1 to 25. In certain embodiments, k is 1 to 20, and l is 1 to 20. Incertain embodiments, k is 1 to 13, and l is 1 to 13. In certainembodiments, k is 1 to 10, and l is 1 to 10. In certain embodiments, k+lranges from 1 to 25. In certain embodiments, k+l ranges from 1 to 13. Incertain embodiments, k+l ranges from 1 to 10. In certain embodiments,k+l is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18,19, 20, 21, 22, 23, 24, or 25.

In certain embodiments, a compound has formula (VI), wherein k and l areeach independently an integer selected from the group consisting of 0 to25, provided that k+l is >0. In certain embodiments, k is 1 to 25, and lis 1 to 25. In certain embodiments, k is 1 to 20, and l is 1 to 20. Incertain embodiments, k is 1 to 13, and l is 1 to 13. In certainembodiments, k is 1 to 10, and l is 1 to 10. In certain embodiments, k+lranges from 1 to 25. In certain embodiments, k+l ranges from 1 to 13. Incertain embodiments, k+l ranges from 1 to 10. In certain embodiments,k+l is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18,19, 20, 21, 22, 23, 24, or 25.

In certain embodiments, a compound has formula (VII), wherein R³, m, andz are as defined above.

The compounds may contain asymmetric centers and can thus occur asracemates and racemic mixtures, single enantiomers, diastereomericmixtures and individual diastereomers. Additional asymmetric centers maybe present depending upon the nature of the various substituents on themolecule. Each such asymmetric center will independently produce twooptical isomers and it is intended that all of the possible opticalisomers and diastereomers in mixtures and as pure or partially purifiedcompounds are included within the scope of this invention. The presentinvention is meant to comprehend all such isomeric forms of thesecompounds.

Michael acceptors refer to α, β-unsaturated electrophiles that mayinclude, but are not limited to, α, β-unsaturated carbonyls,α,β-unsaturated nitriles, α,β-unsaturated aldehydes, α,β-unsaturatedcarboxylic acids, quinones, and α,β-unsaturated sulfones. The Michaelacceptor may include any vinyl derivative substituted with an electronwithdrawing group, such as, but not limited to a nitro group. PossibleMichael acceptors may include, but are not limited to, acrylic acid,dimethyl maleate, crotonaldehyde, 3-butene-2-one, vinyl ketones, alkylvinyl ketones, alkyl acrylates, acrylo nitrile, fumarates, and anycombination thereof.

The compositions disclosed herein include a Michael acceptor and atleast one compound as described above. In certain embodiments, acomposition contains a Michael acceptor and a compound of formula (I).In other embodiments, a composition contains a Michael acceptor and amixture of two or more structurally distinct compounds of formula (I).In certain embodiments, a composition may comprise a Michael acceptorand a mixture of compounds of formula (I), wherein k, l, and/or m arevariable, and/or wherein R¹, R², and/or R³ are variable, and/or whereinx, y, and/or z are variable. In some embodiments, the compositioncomprises at least one or a mixture of Michael acceptors and may containor may not contain other additives or compounds as set forth in thisdisclosure.

In certain embodiments, a composition contains a Michael acceptor and amixture of compounds of formula (I) wherein R¹, R², and R³ are the sameacross the compounds of formula (I) in the composition, respectively,and k, l, and m are optionally variable across the compounds of formula(I) in the composition, respectively. For example, in certainembodiments, a composition includes a Michael acceptor and a mixture ofcompounds of formula (I), wherein R¹, R², and R³ are each unsubstitutedC₂-alkylenyl; k, l, and m are each independently an integer selectedfrom the group consisting of 1 to 25; and x, y, and z are each 1. Incertain embodiments, a composition may include a Michael acceptor and amixture of compounds of formula (I), wherein R¹ and R² are eachunsubstituted C₂-alkylenyl, and R³ is methyl; k and l are eachindependently an integer selected from the group consisting of 1 to 25,and m is absent; and x and y are 1, and z is 0. In certain embodiments,a composition includes a Michael acceptor and a mixture of compounds offormula (I), wherein R¹ and R² are each unsubstituted C₂-alkylenyl, andR³ is hydrogen; k and l are each independently an integer selected fromthe group consisting of 1 to 25, and m is absent; and x and y are 1, andz is 0. In some embodiments, the composition comprises at least one or amixture of distinct Michael acceptors and a compound of formula (I),wherein R¹, R², and R³ are each unsubstituted C₂-alkylenyl; and k, l,and m are each 1. In other embodiments, a composition includes a Michaelacceptor and a compound of formula (III) where k, l, and m are each 1.

All above described compositions may also contain an additive selectedfrom the group consisting of sulfate, sulfate salt, thiosulfate,thiosulfate salt, and any combination thereof. The compositions mayfurther comprise sodium thiosulphate pentahydrate.

In certain embodiments, a composition contains a pure compound offormula (II), a pure compound of formula (III), a pure compound offormula (IV), a pure compound of formula (V), a pure compound of formula(VI), or any combination thereof, wherein the variables of said formulasare as defined above. Such compositions also contain a Michael acceptoror mixture of Michael acceptors.

In certain embodiments, a composition contains a mixture of compounds offormula (II), a mixture of compounds of formula (III), a mixture ofcompounds of formula (IV), a mixture of compounds of formula (V), amixture of compounds of formula (VI), or any combination thereof,wherein the variables of said formulas are as defined above. Suchcompositions also contain a Michael acceptor or mixture of Michaelacceptors.

In certain embodiments, a composition comprises from about 20 to about99 percent by weight of one or more compounds of the invention, or fromabout 20 to about 98 percent by weight of one or more compounds of theinvention, or from about 50 to 97 percent by weight of one or morecompounds of the invention.

In certain embodiments, a composition comprises from about 0.1 to about50 percent by weight of one or more Michael acceptors, from about 0.1 toabout 1 percent by weight, from about 1 to about 5 percent by weight,from about 5 to about 25 percent by weight, from about 5 to about 20percent by weight, from about 5 to about 15 percent by weight, fromabout 5 to about 10 percent by weight, from about 1 to about 20 percentby weight, from about 1 to about 10 percent by weight, from about 3 toabout 20 percent by weight, from about 3 to about 10 percent by weight,from about 25 to about 50 percent by weight, from about 25 to about 40percent by weight, from about 25 to about 35 percent by weight, fromabout 35 to about 50 percent by weight, or from about 40 to about 50percent by weight.

In additional embodiments, the compositions may contain a sulfate,sulfate salt, thiosulfate, thiosulfate salt, or any combination thereof.In some embodiments, the thiosulfate may be sodium thiosulfatepentahydrate.

The compositions can optionally include one or more additives. Suitableadditives include, but are not limited to, asphaltene inhibitors,paraffin inhibitors, corrosion inhibitors, scale inhibitors,emulsifiers, water clarifiers, dispersants, emulsion breakers, hydrogensulfide scavengers, gas hydrate inhibitors, biocides, pH modifiers,surfactants, solvents, and combinations thereof.

Suitable asphaltene inhibitors include, but are not limited to,aliphatic sulphonic acids; alkyl aryl sulphonic acids; aryl sulfonates;lignosulfonates; alkylphenol/aldehyde resins and similar sulfonatedresins; polyolefin esters; polyolefin imides; polyolefin esters withalkyl, alkylenephenyl or alkylenepyridyl functional groups; polyolefinamides; polyolefin amides with alkyl, alkylenephenyl or alkylenepyridylfunctional groups; polyolefin imides with alkyl, alkylenephenyl oralkylenepyridyl functional groups; alkenyl/vinyl pyrrolidone copolymers;graft polymers of polyolefins with maleic anhydride or vinyl imidazole;hyperbranched polyester amides; polyalkoxylated asphaltenes, amphotericfatty acids, salts of alkyl succinates, sorbitan monooleate,polyisobutylene succinic anhydride, and combinations thereof.

Suitable paraffin inhibitors include, but are not limited to, paraffincrystal modifiers, and dispersant/crystal modifier combinations.Suitable paraffin crystal modifiers include, but are not limited to,alkyl acrylate copolymers, alkyl acrylate vinylpyridine copolymers,ethylene vinyl acetate copolymers, maleic anhydride ester copolymers,branched polyethylenes, naphthalene, anthracene, microcrystalline waxand/or asphaltenes, and combinations thereof.

Suitable corrosion inhibitors include, but are not limited to,amidoamines, quaternary amines, amides, phosphate esters, andcombinations thereof.

Suitable scale inhibitors include, but are not limited to, phosphates,phosphate esters, phosphoric acids, phosphonates, phosphonic acids,polyacrylamides, salts of acrylamido-methyl propane sulfonate/acrylicacid copolymer (AMPS/AA), phosphinated maleic copolymer (PHOS/MA), saltsof a polymaleic acid/acrylic acid/acrylamido-methyl propane sulfonateterpolymer (PMA/AMPS), and combinations thereof.

Suitable emulsifiers include, but are not limited to, salts ofcarboxylic acids, products of acylation reactions between carboxylicacids or carboxylic anhydrides and amines, alkyl, acyl and amidederivatives of saccharides (alkyl-saccharide emulsifiers), andcombinations thereof.

Suitable water clarifiers include, but are not limited to, inorganicmetal salts such as alum, aluminum chloride, and aluminum chlorohydrate,or organic polymers such as acrylic acid based polymers, acrylamidebased polymers, polymerized amines, alkanolamines, thiocarbamates,cationic polymers such as diallyldimethylammonium chloride(DADMAC), andcombinations thereof.

Suitable dispersants include, but are not limited to, aliphaticphosphonic acids with 2-50 carbons, such as hydroxyethyl diphosphonicacid, and aminoalkyl phosphonic acids, e.g. polyaminomethylenephosphonates with 2-10 N atoms e.g. each bearing at least one methylenephosphonic acid group; examples of the latter are ethylenediaminetetra(methylene phosphonate), diethylenetriamine penta(methylenephosphonate) and the triamine- and tetramine-polymethylene phosphonateswith 2-4 methylene groups between each N atom, at least 2 of the numbersof methylene groups in each phosphonate being different. Other suitabledispersion agents include lignin or derivatives of lignin such aslignosulfonate and naphthalene sulfonic acid and derivatives, andcombinations thereof.

Suitable emulsion breakers include, but are not limited to,dodecylbenzylsulfonic acid (DDBSA), the sodium salt of xylenesulfonicacid (NAXSA), epoxylated and propoxylated compounds, anionic cationicand nonionic surfactants, resins such as phenolic and epoxide resins,and combinations thereof.

Suitable additional hydrogen sulfide scavengers include, but are notlimited to, oxidants (e.g., inorganic peroxides such as sodium peroxide,or chlorine dioxide), aldehydes (e.g., of 1-10 carbons such asformaldehyde or glutaraldehyde or (meth)acrolein), triazines (e.g.,monoethanol amine triazine, monomethylamine triazine, and triazines frommultiple amines or mixtures thereof), glyoxal, chelated iron, andcombinations thereof.

Suitable gas hydrate inhibitors include, but are not limited to,thermodynamic hydrate inhibitors (THI), kinetic hydrate inhibitors(KHI), anti-agglomerates (AA), and combinations thereof. Suitablethermodynamic hydrate inhibitors include, but are not limited to, NaClsalt, KCl salt, CaCl₂ salt, MgCl₂ salt, NaBr₂ salt, formate brines (e.g.potassium formate), polyols (such as glucose, sucrose, fructose,maltose, lactose, gluconate, monoethylene glycol, diethylene glycol,triethylene glycol, mono-propylene glycol, dipropylene glycol,tripropylene glycols, tetrapropylene glycol, monobutylene glycol,dibutylene glycol, tributylene glycol, glycerol, diglycerol,triglycerol, and sugar alcohols (e.g. sorbitol, mannitol)), methanol,propanol, ethanol, glycol ethers (such as diethyleneglycolmonomethylether, ethyleneglycol monobutylether), alkyl or cyclic estersof alcohols (such as ethyl lactate, butyl lactate, methylethylbenzoate), and combinations thereof. Suitable kinetic hydrate inhibitorsand anti-agglomerates include, but are not limited to, polymers andcopolymers, polysaccharides (such as hydroxy-ethylcellulose (HEC),carboxymethylcellulose (CMC), starch, starch derivatives, and xanthan),lactams (such as polyvinylcaprolactam, polyvinyl lactam), pyrrolidones(such as polyvinyl pyrrolidone of various molecular weights),surfactants (such as fatty acid salts, ethoxylated alcohols,propoxylated alcohols, sorbitan esters, ethoxylated sorbitan esters,polyglycerol esters of fatty acids, alkyl glucosides, alkylpolyglucosides, alkyl sulfates, alkyl sulfonates, alkyl estersulfonates, alkyl aromatic sulfonates, alkyl betaine, alkyl amidobetaines), hydrocarbon based dispersants (such as lignosulfonates,iminodisuccinates, polyaspartates), amino acids, proteins, andcombinations thereof.

Suitable biocides include, but are not limited to, oxidizing andnon-oxidizing biocides. Suitable non-oxidizing biocides include, forexample, aldehydes (e.g., formaldehyde, glutaraldehyde, and acrolein),amine-type compounds (e.g., quaternary amine compounds and cocodiamine),halogenated compounds (e.g., bronopol and2-2-dibromo-3-nitrilopropionamide (DBNPA)), sulfur compounds (e.g.,isothiazolone, carbamates, and metronidazole), quaternary phosphoniumsalts (e.g., tetrakis(hydroxymethyl)phosphonium sulfate (THPS)), andcombinations thereof. Suitable oxidizing biocides include, for example,sodium hypochlorite, trichloroisocyanuric acids, dichloroisocyanuricacid, calcium hypochlorite, lithium hypochlorite, chlorinatedhydantoins, stabilized sodium hypobromite, activated sodium bromide,brominated hydantoins, chlorine dioxide, ozone, peroxides, andcombinations thereof.

Suitable pH modifiers include, but are not limited to, alkalihydroxides, alkali carbonates, alkali bicarbonates, alkaline earth metalhydroxides, alkaline earth metal carbonates, alkaline earth metalbicarbonates and mixtures or combinations thereof. Exemplary pHmodifiers include NaOH, KOH, Ca(OH)₂, CaO, Na₂CO₃, KHCO₃, K₂CO₃, NaHCO₃,MgO, and Mg(OH)₂.

Suitable surfactants include, but are not limited to, anionicsurfactants, cationic surfactants, nonionic surfactants, andcombinations thereof. Anionic surfactants include alkyl aryl sulfonates,olefin sulfonates, paraffin sulfonates, alcohol sulfates, alcohol ethersulfates, alkyl carboxylates and alkyl ether carboxylates, and alkyl andethoxylated alkyl phosphate esters, and mono and dialkyl sulfosuccinatesand sulfosuccinamates, and combinations thereof. Cationic surfactantsinclude alkyl trimethyl quaternary ammonium salts, alkyl dimethyl benzylquaternary ammonium salts, dialkyl dimethyl quaternary ammonium salts,imidazolinium salts, and combinations thereof. Nonionic surfactantsinclude alcohol alkoxylates, alkylphenol alkoxylates, block copolymersof ethylene, propylene and butylene oxides, alkyl dimethyl amine oxides,alkyl-bis(2-hydroxyethyl) amine oxides, alkyl amidopropyl dimethyl amineoxides, alkylamidopropyl-bis(2-hydroxyethyl) amine oxides, alkylpolyglucosides, polyalkoxylated glycerides, sorbitan esters andpolyalkoxylated sorbitan esters, and alkoyl polyethylene glycol estersand diesters, and combinations thereof. Also included are betaines andsultanes, amphoteric surfactants such as alkyl amphoacetates andamphodiacetates, alkyl amphopropripionates and amphodipropionates,alkyliminodiproprionate, and combinations thereof.

In certain embodiments, the surfactant may be a quaternary ammoniumcompound, an amine oxide, an ionic or non-ionic surfactant, or anycombination thereof. Suitable quaternary amine compounds include, butare not limited to, alkyl benzyl ammonium chloride, benzylcocoalkyl(C₁₂-C₁₈)dimethylammonium chloride, dicocoalkyl(C₁₂-C₁₈)dimethylammonium chloride, ditallow dimethylammonium chloride,di(hydrogenated tallow alkyl)dimethyl quaternary ammonium methylchloride, methyl bis(2-hydroxyethyl cocoalkyl(C₁₂-C₁₈) quaternaryammonium chloride, dimethyl(2-ethyl) tallow ammonium methyl sulfate,n-dodecylbenzyldimethylammonium chloride, n-octadecylbenzyldimethylammonium chloride, n-dodecyltrimethylammonium sulfate, soyaalkyltrimethylammonium chloride, and hydrogenated tallow alkyl(2-ethylhyexyl) dimethyl quaternary ammonium methyl sulfate.

Suitable solvents include, but are not limited to, water, isopropanol,methanol, ethanol, 2-ethylhexanol, heavy aromatic naphtha, toluene,ethylene glycol, ethylene glycol monobutyl ether (EGMBE), propyleneglycol monomethyl ether, diethylene glycol monoethyl ether, xylene, andcombinations thereof. Representative polar solvents suitable forformulation with the composition include water, brine, seawater,alcohols (including straight chain or branched aliphatic such asmethanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol,hexanol, octanol, decanol, 2-butoxyethanol, etc.), glycols andderivatives (ethylene glycol, 1,2-propylene glycol, 1,3-propyleneglycol, ethylene glycol monobutyl ether, etc.), ketones (cyclohexanone,diisobutylketone, methyl isobutyl ketone), N-methylpyrrolidinone (NMP),N,N-dimethylformamide and the like. Representative of non-polar solventssuitable for formulation with the composition include aliphatics such aspentane, hexane, cyclohexane, methylcyclohexane, heptane, decane,dodecane, diesel, and the like; aromatics such as toluene, xylene, heavyaromatic naphtha, fatty acid derivatives (acids, esters, amides), andthe like.

In certain embodiments, the solvent is a polyhydroxylated solvent, apolyether, an alcohol, or a combination thereof.

In certain embodiments, the solvent is monoethyleneglycol, methanol,dimethyl sulfoxide (DMSO), dimethylformamide (DMF), tetrahydrofuran(THF), or a combination thereof.

In certain embodiments, a composition comprises from 0 to about 80percent by weight of one or more solvents, based on the weight of thecomposition. In certain embodiments, a composition comprises from 0 toabout 50 percent by weight of one or more solvents, based on the weightof the composition. In certain embodiments, a composition comprises 20%,25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, or 70% by weight of one or moresolvents, based on the weight of the composition.

Compositions made according to the invention may further includeadditional functional agents or additives that provide a beneficialproperty. Additional agents or additives will vary according to theparticular scavenging composition being manufactured and its intend useas one skilled in the art will appreciate. According to one embodiment,the scavenging compositions do not contain any of the additional agentsor additives.

The compositions can be better understood in connection with thefollowing synthetic schemes and methods which illustrate a means bywhich the compounds can be prepared.

Compounds of formula (3) can be prepared as described in Scheme 1,wherein R¹, R², R³, k, l, m, x, y, and z are as defined above. Treatmentof an amine of formula (1) with an aldehyde of formula (2) will providealkanolamine formaldehyde addition products of formula (3). R⁴, R⁵, andR⁶ of formula (1) are each independently selected from hydrogen, alkyl,alkenyl, and alkynyl, provided that at least one of R⁴, R⁵, and R⁶includes at least one hydroxyl group available for reaction with thecompound of formula (2). The aldehyde compound of formula (2) may be amonomeric aldehyde (e.g., formaldehyde) or a polymeric aldehyde (e.g.,paraformaldehyde), wherein n ranges from, for example, 1 to 100. Thecompound of formula (2) can be provided as a solution, such as a 37%aqueous solution or a 50% aqueous solution.

The amine of formula (1) and the aldehyde of formula (2) may be reactedin any suitable molar ratio to provide the desired product. In certainembodiments, the amine:aldehyde reactant molar ratio may range from1:0.25 to 1:25, particularly where paraformaldehyde is used as thealdehyde compound of formula (2). In certain embodiments, theamine:aldehyde reactant molar ratio may be 0.5:20. In certainembodiments, the amine:aldehyde reactant molar ratio may be 1:1. Incertain embodiments, the amine:aldehyde reactant molar ratio may be 1:2.In certain embodiments, the amine:aldehyde reactant molar ratio may be1:3. In certain embodiments, the amine:aldehyde reactant molar ratio maybe 1:4. In certain embodiments, the amine:aldehyde reactant molar ratiomay be 1:5. In certain embodiments, the amine:aldehyde reactant molarratio may be 1:6. In certain embodiments, the amine:aldehyde reactantmolar ratio may be 1:7. In certain embodiments, the amine:aldehydereactant molar ratio may be 1:8. In certain embodiments, theamine:aldehyde reactant molar ratio may be 1:9. In certain embodiments,the amine:aldehyde reactant molar ratio may be 1:10.

In certain embodiments, compounds of formula (3) may be prepared by theaddition of the aldehyde compound of formula (2) to a stirred and heated(e.g., 70-120° C., or 40-100° C.) amine of formula (1). Aqueous additionproducts of formula (3) may be prepared by the reaction of aqueousformalin with an amine of formula (1).

Compounds of formula (3) prepared in aqueous solution may be maintainedas aqueous solutions. Alternatively, in certain embodiments, the watermay be removed and replaced with a different solvent, such asmonoethyleneglycol, methanol, dimethyl sulfoxide (DMSO),dimethylformamide (DMF), or tetrahydrofuran (THF).

In certain embodiments, lower molecular weight addition products offormula (3) may be prepared and may be water miscible.

Anhydrous addition products of formula (3) may be prepared by azeotropicdistillation with azeotropic distillation co-solvents including, but notlimited to, toluene, xylenes, cyclohexane, and heptane. The azeotropicdistillation may be affected by adding 0-50% by weight of solvent to theaddition products of formula (3), and thereafter distilling away thesolvent to azeotropically remove water. Accordingly, in certainembodiments, the compounds of formula (3) may be substantially free ofwater. In certain embodiments, use of paraformaldehyde as the aldehydecompound of formula (2) may be preferred, as paraformaldehydecircumvents water removal processes (e.g., azeotropic distillation),avoids performance deterioration, and lowers manufacturing costs.

In certain embodiments, when one of R¹, R², and R³ is hydrogen,cyclization products, such as those of formula (VII), may be preparedwhen compounds of formula (3) are exposed to elevated temperatures forprolonged periods of time.

In certain embodiments, the addition products may be further modified,for example, by manipulation of substituents. These manipulations mayinclude, but are not limited to, reduction, oxidation, organometalliccross-coupling, alkylation, acylation, and hydrolysis reactions whichare commonly known to those skilled in the art. In some cases, the orderof carrying out the foregoing reaction schemes may be varied tofacilitate the reaction or to avoid unwanted reaction products.

The compositions include compounds produced by a process comprisingtreating an amine of formula (1), described above, with an aldehyde offormula (2), also described above. R⁴, R⁵, and R⁶ of formula (1) areeach independently selected from hydrogen, alkyl, alkenyl, and alkynyl,provided that at least one of R⁴, R⁵, and R⁶ includes at least onehydroxyl group available for reaction with the compound of formula (2).The aldehyde compound of formula (2) may be a monomeric aldehyde (e.g.,formaldehyde) or a polymeric aldehyde (e.g., paraformaldehyde), whereinn ranges from, for example, 1 to 100. The compound of formula (2) can bein solution, such as a 37% aqueous solution or a 50% aqueous solution.The amine of formula (1) and the aldehyde of formula (2) may be reactedin any suitable molar ratio to provide the desired product. In certainembodiments, the amine:aldehyde reactant molar ratio may range from1:0.25 to 1:25, particularly where paraformaldehyde is used as thealdehyde compound of formula (2). In certain embodiments, theamine:aldehyde reactant molar ratio may be 0.5:20. In certainembodiments, the amine:aldehyde reactant molar ratio may be 1:1. Incertain embodiments, the amine:aldehyde reactant molar ratio may be 1:2.In certain embodiments, the amine:aldehyde reactant molar ratio may be1:3. In certain embodiments, the amine:aldehyde reactant molar ratio maybe 1:4. In certain embodiments, the amine:aldehyde reactant molar ratiomay be 1:5. In certain embodiments, the amine:aldehyde reactant molarratio may be 1:6. In certain embodiments, the amine:aldehyde reactantmolar ratio may be 1:7. In certain embodiments, the amine:aldehydereactant molar ratio may be 1:8. In certain embodiments, theamine:aldehyde reactant molar ratio may be 1:9. In certain embodiments,the amine:aldehyde reactant molar ratio may be 1:10.

A product produced by the process may be prepared by the addition of thealdehyde compound of formula (2) to a stirred and heated (e.g., 70-120°C., or 40-100° C.) amine of formula (1). Aqueous addition products maybe prepared by the reaction of aqueous formalin with an amine of formula(1).

In certain embodiments, a compound or composition includes the productof treating 1 molar equivalent of triethanolamine with 3 molarequivalents of paraformaldehyde or formaldehyde. In certain embodiments,a compound or composition includes the product of treating 1 molarequivalent of triethanolamine with 6 molar equivalents ofparaformaldehyde or formaldehyde. In certain embodiments, a compound orcomposition includes the product of treating 1 molar equivalent oftriethanolamine with 9 or 10 molar equivalents of paraformaldehyde orformaldehyde.

In certain embodiments, a compound or composition includes the productof treating 1 molar equivalent of methyldiethanolamine with 3 molarequivalents of paraformaldehyde or formaldehyde. In certain embodiments,a compound or composition includes the product of treating 1 molarequivalent of methyldiethanolamine with 6 molar equivalents ofparaformaldehyde or formaldehyde. In certain embodiments, a compound orcomposition includes the product of treating 1 molar equivalent ofmethyldiethanolamine with 9 or 10 molar equivalents of paraformaldehydeor formaldehyde.

In certain embodiments, a compound or composition includes the productof treating 1 molar equivalent of diethanolamine with 3 molarequivalents of paraformaldehyde or formaldehyde. In certain embodiments,a compound or composition includes the product of treating 1 molarequivalent of diethanolamine with 6 molar equivalents ofparaformaldehyde or formaldehyde. In certain embodiments, a compound orcomposition includes the product of treating 1 molar equivalent ofdiethanolamine with 9 or 10 molar equivalents of paraformaldehyde orformaldehyde.

In certain embodiments, a compound or composition includes the productof treating 1 molar equivalent of triethanolamine with an aqueousformaldehyde solution (e.g., a 37% solution). In certain embodiments, acompound or composition includes the product of treating 1 molarequivalent of methyldiethanolamine with an aqueous formaldehyde solution(e.g., a 37% solution). In certain embodiments, a compound orcomposition includes the product of treating 1 molar equivalent ofdiethanolamine with an aqueous formaldehyde solution (e.g., a 37%solution).

The products produced by the processes disclosed herein may be usedneat, or prepared as compositions comprising one or more additives asdescribed herein. The products may be used in methods of removinghydrogen sulfide and/or mercaptans from a gas or fluid and preventingfouling, as described herein.

The compositions may be used for preventing solid deposits in processequipment and/or for sweetening a gas or liquid. The compositions may beused for scavenging hydrogen sulfide and/or mercaptans from a gas orliquid stream by treating said stream with an effective amount of acompound or composition of the invention, as described herein. Thecompositions can be used in any industry where it is desirable tocapture hydrogen sulfide and/or mercaptans from a gas or liquid streamand prevent solid deposits in process equipment. In certain embodiments,the compositions can be used in water systems, condensate/oilsystems/gas systems, or any combination thereof. In certain embodiments,the compositions can be applied to a gas or liquid produced or used inthe production, transportation, storage, and/or separation of crude oilor natural gas. In certain embodiments, the compositions can be appliedto a gas stream used or produced in a coal-fired process, such as acoal-fired power plant. In certain embodiments, the compositions can beapplied to a gas or liquid produced or used in a waste-water process, afarm, a slaughter house, a land-fill, a municipality waste-water plant,a coking coal process, or a biofuel process. In certain embodiments, thecompositions can be applied to a liquid in a contact tower.

The compositions may be added to any fluid or gas containing hydrogensulfide and/or a mercaptan, or a fluid or gas that may be exposed tohydrogen sulfide and/or a mercaptan. A fluid to which the compositionsmay be introduced may be an aqueous medium. The aqueous medium maycomprise water, gas, and optionally liquid hydrocarbon. A fluid to whichthe compositions may be introduced may be a liquid hydrocarbon. Theliquid hydrocarbon may be any type of liquid hydrocarbon including, butnot limited to, crude oil, heavy oil, processed residual oil, bitminousoil, coker oils, coker gas oils, fluid catalytic cracker feeds, gas oil,naphtha, fluid catalytic cracking slurry, diesel fuel, fuel oil, jetfuel, gasoline, and kerosene. In certain embodiments, the gas may be asour gas. In certain embodiments, the fluid or gas may be a refinedhydrocarbon product.

A fluid or gas treated with a compound or composition may be at anyselected temperature, such as ambient temperature or an elevatedtemperature. In certain embodiments, the fluid (e.g., liquidhydrocarbon) or gas may be at a temperature of from about 40° C. toabout 250° C. In certain embodiments, the fluid or gas may be at atemperature of from −50° C. to 300° C., 0° C. to 200° C., 10° C. to 100°C., or 20° C. to 90° C. In certain embodiments, the fluid or gas may beat a temperature of 22° C., 23° C., 24° C., 25° C., 26° C., 27° C., 28°C., 29° C., 30° C., 31° C., 32° C., 33° C., 34° C., 35° C., 36° C., 37°C., 38° C., 39° C., or 40° C. In certain embodiments, the fluid or gasmay be at a temperature of 85° C., 86° C., 87° C., 88° C., 89° C., 90°C., 91° C., 92° C., 93° C., 94° C., 95° C., 96° C., 97° C., 98° C., 99°C., or 100° C.

The compositions may be added to a fluid at various levels of water cut.For example, the water cut may be from 0% to 100% volume/volume (v/v),from 1% to 80% v/v, or from 1% to 60% v/v. The fluid can be an aqueousmedium that contains various levels of salinity. In one embodiment, thefluid may have a salinity of 0% to 25%, about 1% to 24%, or about 10% to25% weight/weight (w/w) total dissolved solids (TDS).

The fluid or gas in which the compositions are introduced may becontained in and/or exposed to many different types of apparatuses. Forexample, the fluid or gas may be contained in an apparatus thattransports fluid or gas from one point to another, such as an oil and/orgas pipeline. In certain embodiments, the apparatus may be part of anoil and/or gas refinery, such as a pipeline, a separation vessel, adehydration unit, or a gas line. The fluid may be contained in and/orexposed to an apparatus used in oil extraction and/or production, suchas a wellhead. The apparatus may be part of a coal-fired power plant.The apparatus may be a scrubber (e.g., a wet flue gas desulfurizer, aspray dry absorber, a dry sorbent injector, a spray tower, a contact orbubble tower, falling film column, packed column, plate column, rotatingdisc contactor, venture tube, gas-liquid agitated vessel, bubble columnspray tower, or the like). The apparatus may be a cargo vessel, astorage vessel, a holding tank, or a pipeline connecting the tanks,vessels, or processing units. In certain embodiments, the fluid or gasmay be contained in water systems, condensate/oil systems/gas systems,or any combination thereof. In an embodiment, the composition mayprevent solid deposits, for example in any of the above namedapparatuses, and more particularly in a contact tower or contactortower.

The compounds or compositions may be introduced into a fluid or gas byany appropriate method for ensuring dispersal of the scavenger throughthe fluid or gas. The compositions may be injected using mechanicalequipment such as chemical injection pumps, piping tees, injectionfittings, atomizers, quills, and the like. The compositions may beintroduced with or without one or more additional polar or non-polarsolvents depending upon the application and requirements. In certainembodiments, the compositions may be pumped into an oil and/or gaspipeline using an umbilical line. In certain embodiments, capillaryinjection systems can be used to deliver the compositions to a selectedfluid. In certain embodiments, the compositions can be introduced into aliquid and mixed. In certain embodiments, the compositions can beinjected into a gas stream as an aqueous or nonaqueous solution,mixture, or slurry. In certain embodiments, the fluid or gas may bepassed through an absorption tower comprising a compound or compositionof the invention.

The compositions may be applied to a fluid or gas to provide a scavengerconcentration of about 1 parts per million (ppm) to about 1,000,000 ppm,about 1 parts per million (ppm) to about 100,000 ppm, about 10 ppm toabout 75,000 ppm, about 100 ppm to about 45,000 ppm, about 500 ppm toabout 40,000 ppm, about 1,000 ppm to about 35,000 ppm, about 3,000 ppmto about 30,000 ppm, about 4,000 ppm to about 25,000 ppm, about 5,000ppm to about 20,000 ppm, about 6,000 ppm to about 15,000 ppm, or about7,000 ppm to about 10,000 ppm. The compositions may be applied to afluid at a concentration of about 100 ppm to about 2,000 ppm, about 200ppm to about 1,500 ppm, or about 500 ppm to about 1000 ppm. Each systemmay have its own requirements, and a more sour gas (e.g., containingmore hydrogen sulfide) may require a higher dose rate of a compound orcomposition of the invention. In certain embodiments, the compositionsmay be applied to a fluid or gas in an equimolar amount or greaterrelative to hydrogen sulfide and/or mercaptans present in the fluid orgas.

The hydrogen sulfide and/or mercaptan in a fluid or gas may be reducedby any amount by treatment with a compound or composition of theinvention. The actual amount of residual hydrogen sulfide and/ormercaptan after treatment may vary depending on the starting amount. Incertain embodiments, the hydrogen sulfide and/or mercaptan levels may bereduced to about 150 ppm by volume or less, as measured in the vaporphase, based on the volume of the liquid media. In certain embodiments,the hydrogen sulfide levels and/or mercaptan may be reduced to 100 ppmby volume or less, as measured in the vapor phase, based on the volumeof the liquid media. In certain embodiments, the hydrogen sulfide and/ormercaptan levels may be reduced to 50 ppm by volume or less, as measuredin the vapor phase, based on the volume of the liquid media. In certainembodiments, the hydrogen sulfide and/or mercaptan levels may be reducedto 20 ppm by volume or less, as measured in the vapor phase, based onthe volume of the liquid media. In certain embodiments, the hydrogensulfide and/or mercaptan levels may be reduced to 15 ppm by volume orless, as measured in the vapor phase, based on the volume of the liquidmedia. In certain embodiments, the hydrogen sulfide and/or mercaptanlevels may be reduced to 10 ppm by volume or less, as measured in thevapor phase, based on the volume of the liquid media. In certainembodiments, the hydrogen sulfide and/or mercaptan levels may be reducedto 5 ppm by volume or less, as measured in the vapor phase, based on thevolume of the liquid media. In certain embodiments, the hydrogen sulfideand/or mercaptan levels may be reduced to 0 ppm by volume, as measuredin the vapor phase, based on the volume of the liquid media.

In certain embodiments, the compositions may be soluble in an aqueousphase such that the captured sulfur-based species will migrate into theaqueous phase. If an emulsion is present, the captured sulfur-basedspecies can be migrated into the aqueous phase from a hydrocarbon phase(e.g., crude oil) and removed with the aqueous phase. If no emulsion ispresent, a water wash can be added to attract the captured sulfur-basedspecies. In certain embodiments, the compositions can be added before ahydrocarbon (e.g., crude oil) is treated in a desalter, which emulsifiesthe hydrocarbon media with a water wash to extract water solublecontaminants and separates and removes the water phase from thehydrocarbon.

In certain embodiments, a water wash may be added in an amount suitablefor forming an emulsion with a hydrocarbon. In certain embodiments, thewater wash may be added in an amount of from about 1 to about 50 percentby volume based on the volume of the emulsion. In certain embodiments,the wash water may be added in an amount of from about 1 to about 25percent by volume based on the volume of the emulsion. In certainembodiments, the wash water may be added in an amount of from about 1 toabout 10 percent by volume based on the volume of the emulsion. Incertain embodiments, the amount of hydrocarbon may be present in anamount of from about 50 to about 99 percent by volume based on thevolume of the emulsion. In certain embodiments, the hydrocarbon may bepresent in an amount of from about 75 to about 99 percent by volumebased on the volume of the emulsion. In certain embodiments, thehydrocarbon may be present in an amount of from about 90 to about 99percent by volume based on the volume of the emulsion.

The water wash and hydrocarbon may be emulsified by any conventionalmanner. In certain embodiments, the water wash and hydrocarbon may beheated and thoroughly mixed to produce an oil-in-water emulsion. Incertain embodiments, the water wash and hydrocarbon may be heated at atemperature in a range of from about 90° C. to about 150° C. The waterwash and hydrocarbon may be mixed in any conventional manner, such as anin-line static mixer or an in-line mix valve with a pressure drop ofabout 0.2 to about 2 bar depending on the density of the hydrocarbon.The emulsion may be allowed to separate, such as by settling, into anaqueous phase and an oil phase. In certain embodiments, the aqueousphase may be removed. In another embodiment, the aqueous phase may beremoved by draining the aqueous phase.

Optionally, demulsifiers may be added to aid in separating water fromthe hydrocarbon. In certain embodiments, the demulsifiers include, butare not limited to, oxyalkylated organic compounds, anionic surfactants,nonionic surfactants or mixtures of these materials. The oxyalkylatedorganic compounds include, but are not limited to, phenolformaldehyderesin ethoxylates and alkoxylated polyols. The anionic surfactantsinclude alkyl or aryl sulfonates, such as dodecylbenzenesulfonate. Thesedemulsifiers may be added in amounts to contact the water from about 1to about 1000 ppm by weight based on the weight of the hydrocarbon.

The compounds, compositions, methods, and processes will be betterunderstood by reference to the following examples, which are intended asan illustration of and not a limitation upon the scope of the invention.

The foregoing may be better understood by reference to the followingexamples, which are presented for purposes of illustration and are notintended to limit the scope of the invention.

a. Compounds and Compositions

Example 1 Triethanolamine Formaldehyde Addition Product (3:1Aldehyde:Amine Mole Ratio)

Paraformaldehyde and triethanolamine (TEA) were charged in a 3:1 moleratio into a 1000 mL four-neck round-bottom flask and heated withstirring to 80-100° C. slowly over a period of 1.5 hours under an inertatmosphere to prevent discoloration. After the paraformaldehyde wascompletely dissolved and/or reacted the heating was stopped and cooledto room temperature to yield triethanolamine formaldehyde additionproduct in quantitate yield.

Example 2 Triethanolamine Formaldehyde Addition Product (6:1Aldehyde:Amine Mole Ratio)

Paraformaldehyde and triethanolamine (TEA) were charged in a 6:1 moleratio into a 1000 mL four-neck round-bottom flask and heated withstirring to 80-100° C. slowly over a period of 2.0 hours under an inertatmosphere to prevent discoloration. After the paraformaldehyde wascompletely dissolved and/or reacted the heating was stopped and cooledto room temperature to yield triethanolamine formaldehyde additionproduct in quantitate yield.

Example 3 Triethanolamine Formaldehyde Addition Product (10:1Aldehyde:Amine Mole Ratio)

Paraformaldehyde was slowly charged in portions to triethanolamine (TEA)in a 1000 mL four-neck round-bottom flask with stirring and heating to90-100° C. under an inert atmosphere to prevent discoloration until amolar ratio of 10:1 was met. At no time did the reaction temperatureexceed 100° C. After the paraformaldehyde was completely dissolvedand/or reacted the heating was stopped and cooled to room temperature toyield triethanolamine formaldehyde addition product in quantitate yield.

Example 4 Methyldiethanolamine Formaldehyde Addition Product (2:1Aldehyde:Amine Mole Ratio)

Paraformaldehyde and methyldiethanolamine (MDEA) were charged in a 2:1mole ratio into a 1000 mL four-neck round-bottom flask and heated withstirring to 80-100° C. slowly over a period of 1.5 hours under an inertatmosphere to prevent discoloration. After the paraformaldehyde wascompletely dissolved and/or reacted the heating was stopped and cooledto room temperature to yield methyldiethanolamine formaldehyde additionproduct in quantitate yield.

Example 5 Methyldiethanolamine Formaldehyde Addition Product (4:1Aldehyde:Amine Mole Ratio)

Paraformaldehyde and methyldiethanolamine (MDEA) are charged in a 4:1mole ratio into a 1000 mL four-neck round-bottom flask and heated withstirring to 70-90° C. slowly over a period of 2.0 hours under an inertatmosphere to prevent discoloration. After the paraformaldehyde iscompletely dissolved and/or reacted the heating is stopped and cooled toroom temperature to yield methyldiethanolamine formaldehyde additionproduct in quantitate yield.

Example 6 Methyldiethanolamine Formaldehyde Addition Product (6:1Aldehyde:Amine Mole Ratio)

Paraformaldehyde is slowly charged in portions to methyldiethanolamine(MDEA) in a 1000 mL four-neck round-bottom flask with stirring andheating to 90-100° C. under an inert atmosphere to prevent discolorationuntil a molar ratio of 6:1 is met. At no time does the reactiontemperature exceed 100° C. After the paraformaldehyde is completelydissolved and/or reacted the heating is stopped and cooled to roomtemperature to yield methyldiethanolamine formaldehyde addition productin quantitate yield.

Example 7

Triethanolamine Formaldehyde Addition Product from Aqueous Formaldehydeand Triethanolamine (3:1 Aldehyde:Amine Mole Ratio)

250 g of an aqueous formaldehyde solution (37%) was charged to afour-neck 100 mL flask and stirred. 150 g of triethanolamine (TEA) wasadded at a constant rate maintaining a reaction temperature of less than90° C. The reaction was mildly exothermic. After the TEA addition wascomplete, 5-10% of toluene was added to the reaction vessel and heatedwith stirring to the temperature where toluene and water azeotropicallydistilled (85-90° C.). After the quantitative amount of water wasremoved from the reaction by azeotropic distillation, the reactiontemperature was raised to 95-115° C. such that any remaining toluene wasdistilled and removed, providing the triethanolamine formaldehydeaddition product in quantitative yield.

Example 8

Methyldiethanolamine Formaldehyde Addition Product from AqueousFormaldehyde and Methyldiethanolamine (2:1 Aldehyde:Amine Mole Ratio)

164 g of an aqueous formaldehyde solution (37%) is charged to afour-neck 100 mL flask and stirred. 119 g of methyldiethanolamine (MDEA)is added at a constant rate maintaining a reaction temperature of lessthan 90° C. The reaction is mildly exothermic. After the MDEA additionis complete, 5-10% of toluene is added to the reaction vessel and heatedwith stirring to the temperature where toluene and water areazeotropically distilled (85-90° C.). After the quantitative amount ofwater is removed from the reaction by azeotropic distillation, thereaction temperature is raised to 95-115° C. such that any remainingtoluene is distilled and removed, providing the anhydrousmethyldiethanolamine formaldehyde addition product in quantitativeyield.

Example 9

Diethanolamine Formaldehyde Addition Product from Paraformaldehyde andDiethanolamine (2:1 Aldehyde:Amine Mole Ratio & 3:1 Aldehyde:Amine MoleRatio)

Paraformaldehyde is dispersed in toluene (5-10 wt. %) and heated to85-90° C. while stirring. Diethanolamine is added at a constant ratemaintaining a reaction temperature of less than 90° C. After all thediethanolamine is added, the reaction is allowed to continue to heat at85-90° C. for 30-35 minutes. The reaction temperature is increased to100° C. where toluene and water of reaction are azeotropically distilled(85-90° C.). After the quantitative amount of water is removed from thereaction by azeotropic distillation, the reaction temperature is raisedto 95-115° C. such that any remaining toluene is distilled and removed,providing the diethanolamine formaldehyde addition product inquantitative yield.

Care is taken to avoid temperatures of more than 120° C. to avoiddegradation of the addition product. Sparging the fluids with an inertgas may be used to remove the last traces of toluene. Analysis mayindicate the presence of diethanolamine formaldehyde addition product,as well as cycliclized products of formula (VII), shown above.

Example 10

Diethanolamine Formaldehyde Addition Product from Paraformaldehyde andDiethanolamine

Paraformaldehyde was heated to 70-75° C. while stirring. Diethanolaminewas added at a constant rate maintaining a reaction temperature of lessthan 75° C. After all the diethanolamine was added, the reaction wasallowed to continue to stir at 75° C. for 30-35 minutes. Thediethanolamine formaldehyde addition product was isolated inquantitative yield.

Care was taken to avoid temperatures of more than 75° C. to avoiddegradation and/or cyclization of the addition products. Analysisindicated the presence of diethanolamine formaldehyde addition product,as well as minimal cycliclized product of formula (VII), shown above.

Example 11

Diethanolamine Formaldehyde Addition Product from Aqueous Formaldehydeand Diethanolamine (2:1 Aldehyde:Amine Mole Ratio & 3:1 Aldehyde:AmineMole Ratio)

An aqueous formaldehyde solution (37%) is mixed with toluene (5-10 wt.%) and heated to 85-90° C. while stirring. Diethanolamine is added at aconstant rate maintaining a reaction temperature of less than 90° C.After all the diethanolamine is added, the reaction continues to heat at85-90° C. for 30-35 minutes. The reaction temperature is increased to100° C. where toluene and water of reaction azeotropically distill(85-90° C.). After the quantitative amount of water is removed from thereaction by azeotropic distillation, the reaction temperature is raisedto 95-115° C. such that any remaining toluene is distilled and removedfrom the addition product, providing the product in quantitative yield.

Care is taken to avoid temperatures of more than 120° C. to avoiddegradation of the addition product. Sparging the fluids with an inertgas may be used to remove the last traces of toluene. Analysis mayindicate the presence of diethanolamine formaldehyde addition product,as well as cycliclized product of formula (VII), as shown above.

Example 12

Dimethylmonoethanolamine Formaldehyde Addition Product fromParaformaldehyde and Dimethylmonoethanolamine (1:1 Aldehyde:Amine MoleRatio)

Formulations of the compositions were prepared and evaluated forhydrogen sulfide scavenging ability. The formulations prepared includeneat formulations of the alkanolamine formaldehyde addition products;formulations of alkanolamine formaldehyde addition products and one ormore solvents; formulations of alkanolamine formaldehyde additionproducts and one or more surfactant compounds; and combinations thereof.Table 1 shows Formulations prepared and evaluated for scavengingability.

TABLE 1 Formulation Formulation Description Formulation 1 Example 1 (3:1Formaldehyde:Triethanolamine Mole Ratio), formulated with 35% water, byweight Formulation 2 Example 1 (3:1 Formaldehyde:Triethanolamine MoleRatio) formulated with 28% water, by weight Formulation 3 Example 3(10:1 Formaldehyde:Triethanolamine Mole Ratio) formulated with 38%water, by weight Formulation 4 Example 3 (10:1Formaldehyde:Triethanolamine Mole Ratio) formulated with 20%monoethylene glycol, by weight Formulation 5 Example 1 (3:1Formaldehyde:Triethanolamine Mole Ratio) that is solvent freeFormulation 6 Example 1 (3:1 Formaldehyde:Triethanolamine Mole Ratio)formulated with water Formulation 7 Example 2 (6:1Formaldehyde:Triethanolamine Mole Ratio) formulated with waterFormulation 8 Example 3 (9:1 Formaldehyde:Triethanolamine Mole Ratio)formulated with water Formulation 9 Example 1 (3:1Formaldehyde:Triethanolamine Mole Ratio) formulated with 5% cocoaminesulfate quat, and 35% water, by weight Formulation 10 Example 3 (10:1Formaldehyde:Triethanolamine Mole Ratio) formulated with 20% ethyleneglycol, 50% water, and 5% cocoamine methylsulfate quat, by weightFormulation 11 Example 3 (10:1 Formaldehyde:Triethanolamine Mole Ratio)formulated with 20% ethylene glycol, 40% water, and 5% cocoaminechloride quat, by weight Formulation 12 Example 3 (10:1Formaldehyde:Triethanolamine Mole Ratio) formulated with 20% ethyleneglycol, and 6.5% cocoamine methylsulfate quat, by weight Formulation 13Example 3 (10:1 Formaldehyde:Triethanolamine Mole Ratio) formulated with20% ethylene glycol, and 5% cocoamine chloride quat, by weightFormulation 14 Example 1 (3:1 Formaldehyde:Triethanolamine Mole Ratio)formulated with 8% cocoamine methyl sulfate quat, and 28% water, byweight Formulation 15 Example 1 (3:1 Formaldehyde:Triethanolamine MoleRatio) formulated with 7% cocoamine chloride quat, and 25% water, byweight Formulation 16 Example 1 (3:1 Formaldehyde:Triethanolamine MoleRatio) formulated with 6% cocoamine benzyl chloride quat, and 35% water,by weight

Table 2 shows the dose response profile of the product of Example 1formulated with 35% by weight water to aid in the dispersion of thescavenger (Formulation 1). The test was conducted using kerosene at 22°C. containing 1200 ppm of hydrogen sulfide in the vapor. The amount ofhydrogen sulfide in the vapor was measured using a ½ full 1 quartcontainer using Draeger Tubes to measure the amount of hydrogen sulfidein the vapor. Formulation 1 was added to the bottle followed by thekerosene containing H₂S. The samples were vigorously shaken for 30seconds and then set at room temperature for 2 hours. After 2 hours, thesample was shaken vigorously for 30 seconds and then tested with aDraeger tube.

TABLE 2 Sample Initial H₂S Final H₂S Dose Dose % Description ppm ppm ppmRatio Reduction Untreated 1200 — — 0 — Formulation 1 1200 800 120 0.133.3 Formulation 1 1200 800 240 0.2 33.3 Formulation 1 1200 650 360 0.345.8 Formulation 1 1200 575 480 0.4 52.1 Formulation 1 1200 500 600 0.558.3 Formulation 1 1200 300 1200  1 75.0

Table 3 shows comparison of different hydrogen sulfide scavengingformulations at fixed doses in kerosene. Formulation 2 is the product ofExample 1 (3:1 Aldehyde:Amine Mole Ratio) formulated with 28% water.Formulation 3 is the product of Example 3 (10:1 Aldehyde:Amine MoleRatio) formulated with 38% water. Formulation 4 is the product ofExample 3 (10:1 Aldehyde:Amine Mole Ratio) formulated with 20%monoethylene glycol. Formulation 5 is the product of Example 1 (3:1Aldehyde:Amine Mole Ratio) that is solvent free.

The tests were conducted using kerosene that contained 1300 ppm ofhydrogen sulfide in the vapor. The amount of hydrogen sulfide in thevapor was measured using a ½ full 1 quart container using Draeger Tubesto measure the amount of hydrogen sulfide in the vapor. The formulationswere each added to a fresh bottle followed by 500 mL of kerosenecontaining H₂S. The samples were sealed and vigorously shaken for 30seconds and then set at room temperature for 1.5 hours. After 2 hoursthe samples were shaken vigorously for 30 seconds and then tested with aDraeger tube.

TABLE 3 Sample Initial H₂S Final H₂S Dose Dose % Description ppm ppm ppmRatio Reduction Untreated 1300 — — 0 — Formulation 2 1300 500 650 0.561.5 Formulation 3 1300 600 650 0.5 53.8 Formulation 4 1300 800 650 0.538.5 Formulation 5 1300 700 650 0.5 46.1

Table 4 shows comparison of Formulations 6-8 at a 0.05 dose rose ratioin fuel oil heated to 90° C. Formulation 6 is the product of Example 1formulated with water. Formulation 7 is the product of Example 2formulated with water. Formulation 8 is the product of the reaction of 9moles of formaldehyde with 1 mole of triethanolamine, and containswater.

The tests were conducted using fuel oil that contained 2400 ppm ofhydrogen sulfide in the vapor. The amount of hydrogen sulfide in thevapor was measured using a ½ full 1 quart container using Draeger Tubesto measure the amount of hydrogen sulfide in the vapor. The formulationswere each added to a fresh sample container followed by 500 mL of thefuel oil containing H₂S. The samples were sealed and vigorously shakenfor 30 seconds and then placed in an oven set at 90° C. for 2 hours.After 2 hours the samples were shaken vigorously for 30 seconds and thentested with a Draeger tube.

TABLE 4 Sample Initial H₂S Final H₂S Dose Dose % Description ppm ppm ppmRatio Reduction Untreated 2400 — — 0 — Formulation 6 2400  700 120 0.0571.0 Formulation 7 2400 1000 120 0.05 58.0 Formulation 8 2400 1375 1200.05 43.0

Table 5 shows comparison of Formulations 6-8 at a dose ratio of 0.1 inwater at 22° C. The water containing 1000 ppm of H₂S was placed in a 500mL bottle with a stir bar and the H₂S was measured after 15 minutes. Theformulations were each added to a fresh bottle and 250 mL of water wasadded with stirring. After 15 minutes the cap was removed and the vaporspace H₂S measured using a Draeger tube.

TABLE 5 Sample Initial H₂S Final H₂S Dose Dose % Description ppm ppm ppmRatio Reduction Untreated 1000 — — 0 — Formulation 6 1000 425 100 0.157.5 Formulation 7 1000 675 100 0.1 32.5 Formulation 8 1000 800 100 0.120.0

Table 6 shows the dose response profile of the product of Example 1formulated with 35% water and a quaternary amine surfactant (Formulation9). The test was conducted using kerosene at 22° C. containing 1100 ppmof hydrogen sulfide in the vapor. The amount of hydrogen sulfide in thevapor was measured using a ½ full 1 quart container using Draeger Tubesto measure the amount of hydrogen sulfide in the vapor. Formulation 9(3:1 Formaldehyde:TEA, formulated with 5% cocoamine sulfate quat with35% water) was added to a fresh bottle followed by 500 mL of thekerosene containing H₂S. The samples were sealed and vigorously shakenfor 30 seconds and then set at room temperature for 2 hours. After 2hours the sample was shaken vigorously for 30 seconds and then testedwith a Draeger tube.

TABLE 6 Sample Initial H₂S Final H₂S Dose Dose % Description ppm ppm ppmRatio Reduction Untreated 1100 — — 0 — Formulation 9 1100 220 110 0.172.7 Formulation 9 1100 40 220 0.2 96.4 Formulation 9 1100 10 330 0.399.1 Formulation 9 1100 5 440 0.4 99.5 Formulation 9 1100 2 550 0.5 99.8

Table 7 shows the dose response profile of the product of Example 3formulated with 20% ethylene glycol, 50% water, and 5% quaternary amine(Formulation 10). The test was conducted using kerosene at 22° C.containing 2100 ppm of hydrogen sulfide in the vapor. The amount ofhydrogen sulfide in the vapor was measured using a ½ full 1 quartcontainer using Draeger Tubes to measure the amount of hydrogen sulfidein the vapor. Formulation 10 (10:1 Formaldehyde:TEA, formulated with 20%ethylene glycol, 50% water, and 5% cocoamine methylsulfate quat) wasadded to a fresh bottle followed by 500 mL of the kerosene containingH₂S. The samples were sealed and vigorously shaken for 30 seconds andthen set at room temperature for 2 hours. After 2 hours the sample wasshaken vigorously for 30 seconds and then tested with a Draeger tube.

TABLE 7 Sample Initial H₂S Final H₂S Dose Dose % Description ppm ppm ppmRatio Reduction Untreated 2100 — — 0 — Formulation 10 2100 220 210 0.189.5 Formulation 10 2100 70 420 0.2 96.7 Formulation 10 2100 20 630 0.399.0 Formulation 10 2100 5 840 0.4 99.8

Table 8 shows hydrogen sulfide scavenging ability of Formulations 10-13at a dose ratio of 1.0. The tests were conducted using kerosene at 35°C. containing 1900 ppm of hydrogen sulfide in the vapor; and at a 1.0dose ratio for each formulation and a residence time of 30 minutes.

TABLE 8 Sample Initial H₂S Final H₂S Dose Dose % Description ppm ppm ppmRatio Reduction Untreated 1900 — — 0 — Formulation 10 1900 0 1900 1100.0 Formulation 11 1900 0 1900 1 100.0 Formulation 12 1900 0 1900 1100.0 Formulation 13 1900 10 1900 1  99.5

Table 9 shows hydrogen sulfide scavenging ability of Formulations 10,11, 14, and 15 at a dose ratio of 0.5. The tests were conducted usingkerosene at 22° C. containing 2100 ppm of hydrogen sulfide in the vapor;and at a 0.5 dose ratio for each formulation and a residence time of1.25 hours.

TABLE 9 Sample Initial H₂S Final H₂S Dose Dose % Description ppm ppm ppmRatio Reduction Untreated 2100 — — 0 — Formulation 10 2100 0 1050 0.5100.0  Formulation 11 2100 70 1050 0.5 96.7 Formulation 14 2100 10 10500.5 99.5 Formulation 15 2100 220 1050 0.5 89.5

Table 10 shows the dose response profile of Formulation 16 in fuel oilat 90° C., ca. 16 hours. The tests show excellent performance ofFormulation 16 for scavenging hydrogen sulfide from the fuel oil.

TABLE 10 Sample Initial H₂S Dose Dose Amt H₂S % Description ppm ppmRatio Reduced Reduction Formulation 16 2000 600 0.3 1990 99.5Formulation 16 2000 1200 0.6 1998 99.9 Formulation 16 2000 1800 0.9 2000100.0 Formulation 16 2000 2400 1.2 2000 100.0

Table 11 shows various formulations tested for preventing solid depositsin contact tower reaction product waste. Formation of solid deposits wastested using five different formulations. Various cosolvents wereincluded in the formulation, namely monoethylene glycol (Formulation 17,12.5%; Formulation 18, 17.5%; Formulation 19, 17.5%; Formulation 20,17.5%; Formulation 21, 10%), methanol (Formulation 17, 15%; Formulation18, 20%, Formulation 19, 20%, Formulation 20, 20%), water (Formulation17, 19%; Formulation 18, 19%, Formulation 19, 17%, Formulation 21, 30%),ethylene glycol monobutyl ether (Formulation 17, 10%), methyl isobutylketone (Formulation 20, 19.5%), isopropyl alcohol (Formulation 21, 5%),and propylene glycol monomethyl ether (Formulation 21, 10%).Formulations 17-19 included an anionic scale inhibitor. The formulationswere run through a simulated contact tower. The spent fluid was thenadded to jars for monitoring of solid formation. The above percentagesrefer to weight percent.

The spent scavenger solutions containing scavenging compounds disclosedin this application develop solids within 24 hours upon standing.However, when the formulation included Michael acceptors, the clarity ofthe spent scavenger solution extended to over 10 days. Formulations 1-4(Table 11) without a Michael acceptor developed concrete-like depositsafter 24 h, whereas formulation 5 showed zero formation of solids andthe solution remained clear. Sodium thiosulfate pentahydrate furtherextended the clarity of the solution past 10 days a few additional dayswhen included in the formulation. Mixtures of Michael acceptors (5% byweight acrylic acid and 5% by weight dimethyl maleate) also preventedformation of solid deposits.

TABLE 11 Formu- H₂S Hydro- Scale Acrylic Solid lation Scavenger Solventquinone Inhibitor Acid Deposits 17 40 56.5 1 2.5 0 Yes 18 40 56.5 1 2.50 Yes 19 40 54.5 3 2.5 0 Yes 20 40 57 3 0 0 Yes 21 35 55 0 0 10 None

Using the claimed composition ensures uninterrupted operation ofscavenging process units, for example contact towers, without the needto shut down the unit to remove solid deposits.

All of the compositions and methods disclosed and claimed herein can bemade and executed without undue experimentation in light of the presentdisclosure. While this invention may be embodied in many differentforms, there are described in detail herein specific preferredembodiments of the invention. The present disclosure is anexemplification of the principles of the invention and is not intendedto limit the invention to the particular embodiments illustrated. Inaddition, unless expressly stated to the contrary, use of the term “a”is intended to include “at least one” or “one or more.” For example, “adevice” is intended to include “at least one device” or “one or moredevices.”

Any ranges given either in absolute terms or in approximate terms areintended to encompass both, and any definitions used herein are intendedto be clarifying and not limiting. Notwithstanding that the numericalranges and parameters setting forth the broad scope of the invention areapproximations, the numerical values set forth in the specific examplesare reported as precisely as possible. Any numerical value, however,inherently contains certain errors necessarily resulting from thestandard deviation found in their respective testing measurements.Moreover, all ranges disclosed herein are to be understood to encompassany and all subranges (including all fractional and whole values)subsumed therein.

Furthermore, the invention encompasses any and all possible combinationsof some or all of the various embodiments described herein. It shouldalso be understood that various changes and modifications to thepresently preferred embodiments described herein will be apparent tothose skilled in the art. Such changes and modifications can be madewithout departing from the spirit and scope of the invention and withoutdiminishing its intended advantages. It is therefore intended that suchchanges and modifications be covered by the appended claims.

What is claimed is:
 1. A composition, comprising: a Michael acceptor;and one or more compounds of formula (I),

wherein R¹, R², and R³ are each independently selected from the groupconsisting of hydrogen, alkylenyl, alkenylenyl, alkynylenyl, alkyl,alkenyl, and alkynyl, wherein said alkylenyl, alkenylenyl, alkynylenyl,alkyl, alkenyl, and alkynyl are each independently, at each occurrence,substituted or unsubstituted with one or more suitable substituents; k,l, and m are each independently an integer selected from the groupconsisting of 0 to 25, wherein k+l+m is >0; and x, y, and z are eachindependently an integer selected from the group consisting of 0 and 1,wherein x+y+z is 1, 2, or 3; provided that: when x is 0, R¹ is hydrogen,alkyl, alkenyl, or alkynyl; and when x is 1, R¹ is alkylenyl,alkenylenyl, or alkynylenyl; when y is 0, R² is hydrogen, alkyl,alkenyl, or alkynyl; and when y is 1, R² is alkylenyl, alkenylenyl, oralkynylenyl; when z is 0, R³ is hydrogen, alkyl, alkenyl, or alkynyl;and when z is 1, R³ is alkylenyl, alkenylenyl, or alkynylenyl; and whenx is 1, y is 1, z is 1, k is 1, l is 1, and m is 1, then R¹, R², and R³are not simultaneously unsubstituted C₂-alkylenyl.
 2. The composition ofclaim 1, wherein x+y+z is 3, and R¹, R², and R³ are each selected fromthe group consisting of alkylenyl, C₂-alkylenyl, unsubstitutedC₂-alkylenyl, and any combination thereof.
 3. The composition of claim1, wherein x is 1, y is 1, z is 0, R¹ and R² are each alkylenyl, and R³is alkyl.
 4. The composition of claim 1, wherein x is 1, y is 1, z is 0,R¹ and R² are each C₂-alkylenyl, and R³ is C₁-alkyl.
 5. The compositionof claim 1, wherein x is 1, y is 1, z is 0, R¹ and R² are eachunsubstituted C₂-alkylenyl, and R³ is unsubstituted C₁-alkyl.
 6. Thecomposition of claim 1, wherein x is 1, y is 1, z is 0, R¹ and R² areeach alkylenyl, and R³ is hydrogen.
 7. The composition of claim 1,wherein x is 1, y is 1, z is 0, R¹ and R² are each C₂-alkylenyl, and R³is hydrogen.
 8. The composition of claim 1, wherein x is 1, y is 1, z is0, R¹ and R² are each unsubstituted C₂-alkylenyl, and R³ is hydrogen. 9.The composition of claim 1, wherein the compound is of formula (II),

wherein R³ is selected from the group consisting of hydrogen, alkylenyl,alkenylenyl, alkynylenyl, alkyl, alkenyl, and alkynyl, wherein saidalkylenyl, alkenylenyl, alkynylenyl, alkyl, alkenyl, and alkynyl areeach independently substituted or unsubstituted with one or moresuitable substituents; k, l, and m are each independently an integerselected from the group consisting of 0 to 25, wherein k+l+m is >0; andz is 0 or 1; provided that: when z is 1, R³ is alkylenyl, alkenylenyl,or alkynylenyl; when z is 0, R³ is hydrogen, alkyl, alkenyl, or alkynyl;and when z is 1, k is 1, l is 1, and m is 1, then R³ is not anunsubstituted C₂-alkylenyl.
 10. The composition of claim 1, wherein thecompound is of formula (III)

wherein k, l, and m are each
 1. 11. The composition of claim 1, whereinthe Michael acceptor is an α, β-unsaturated carbonyl compound.
 12. Thecomposition of claim 1, wherein the Michael acceptor is selected fromthe group consisting of acrylic acid, acrylamide, methacrylate, dimethylmaleate, crotonaldehyde, 3-butene-2-one, and any combination thereof.13. The composition of claim 1, wherein the Michael acceptor is acrylicacid.
 14. The composition of claim 1, further comprising sodiumthiosulfate pentahydrate.
 15. A method, comprising: adding a compositionto a fluid or gas, the composition comprising: a Michael acceptor andone or more compounds of formula (I),

wherein R¹, R², and R³ are each independently selected from the groupconsisting of hydrogen, alkylenyl, alkenylenyl, alkynylenyl, alkyl,alkenyl, and alkynyl, wherein said alkylenyl, alkenylenyl, alkynylenyl,alkyl, alkenyl, and alkynyl are each independently, at each occurrence,substituted or unsubstituted with one or more suitable substituents; k,l, and m are each independently an integer selected from the groupconsisting of 0 to 25, wherein k+l+m is >0; and x, y, and z are eachindependently an integer selected from the group consisting of 0 and 1,wherein x+y+z is 1, 2, or 3; provided that: when x is 0, R¹ is hydrogen,alkyl, alkenyl, or alkynyl; and when x is 1, R¹ is alkylenyl,alkenylenyl, or alkynylenyl; when y is 0, R² is hydrogen, alkyl,alkenyl, or alkynyl; and when y is 1, R² is alkylenyl, alkenylenyl, oralkynylenyl; and when z is 0, R³ is hydrogen, alkyl, alkenyl, oralkynyl; and when z is 1, R³ is alkylenyl, alkenylenyl, or alkynylenyl.16. The method of claim 15, wherein x+y+z is 3, and R¹, R², and R³ areeach selected from the group consisting of alkylenyl, C₂-alkylenyl,unsubstituted C₂-alkylenyl, and any combination thereof.
 17. The methodof claim 15, wherein the Michael acceptor is selected from the groupconsisting of acrylic acid, acrylamide, methacrylate, dimethyl maleate,crotonaldehyde, 3-butene-2-one, and any combination thereof.
 18. Themethod of claim 15, wherein the composition is added to a liquid in aprocess unit selected from the group consisting of a falling filmcolumn, a bubble column spray tower, a gas-liquid agitated vessel, aplate column, a rotating disc contactor, a contact tower, a wet flue gasdesulfurizer, a spray dry absorber, a dry sorbent injector, a spraytower, a bubble tower and a venturi tube.
 19. The method of claim 15,wherein the composition is added to a liquid in a contact tower.